Organic hydrogen storage raw material dehydrogenation catalyst, carrier of catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen gas

ABSTRACT

A catalyst used for dehydrogenation of an organic hydrogen-storage material to generate hydrogen, a support for the catalyst, and a preparation process thereof are presented. A hydrogen-storage alloy and a preparation process thereof are provided. A process for providing high-purity hydrogen, a high-efficiently distributed process for producing high-purity and high-pressure hydrogen, a system for providing high-purity and high-pressure hydrogen, a mobile hydrogen supply system, and a distributed hydrogen supply apparatus are also described.

TECHNICAL FIELD

The present invention relates to a catalyst used for dehydrogenation ofan organic hydrogen-storage material to generate hydrogen gas, a supportfor the catalyst, and a preparation process thereof; the presentinvention also relates to a hydrogen-storage alloy and a preparationprocess thereof; and the present invention also relates to a process forproviding high-purity hydrogen gas, a high-efficiently distributedprocess for producing high-purity and high-pressure hydrogen gas, asystem for providing high-purity and high-pressure hydrogen gas, amobile hydrogen supply system, and a distributed hydrogen supplyapparatus.

BACKGROUND TECHNOLOGY

As a renewable energy source, hydrogen gas is not only energy efficient,but also produces almost no waste. The development of hydrogen gasenergy source is expected to become an important way to improve energyefficiency, reduce oil consumption, improve the ecological environment,and ensure energy security. The development of sustainable and efficientlarge-scale hydrogen production technology has become an urgent need inthe hydrogen energy era.

Hydrogen gas exists in gaseous form under normal conditions, and isflammable, explosive, and easy to diffuse, so that people should givepriority to safety, high efficiency and no leakage loss inhydrogen-storage and transportation in practical applications, whichbrings great difficulties in storage and transportation. Therefore,hydrogen energy utilization needs to solve the problem of hydrogen gasstorage and transportation.

Hydrogen gas is directly transported from the production site to thehydrogen fueling station in high-pressure gaseous state. Thetransportation cost is high, and long-distance transportation also hascertain traffic safety hazards. In case of storing hydrogen gas inhigh-pressure gas state, the cost and the area of hydrogen-storage tanksare high and large, and there are also major safety hazards.

SUMMARY OF THE INVENTION

A technical problem to be solved by the present invention is to providea catalyst for dehydrogenation of an organic hydrogen-storage compoundto prepare hydrogen gas and a support for the catalyst. Anothertechnical problem to be solved by the present invention is to provide ahydrogen-storage alloy used in a process for purifying a hydrogen gascontaining organic substances and a preparation process thereof. Anothertechnical problem to be solved by the present invention is to provide aprocess for providing high-purity hydrogen gas, a high-efficientlydistributed process for producing high-purity and high-pressure hydrogengas, a system for providing high-purity and high-pressure hydrogen gas,and a mobile hydrogen supply system and a distributed hydrogen supplyapparatus:

To this end, the present invention provides the following technicalsolutions:

1. A process of providing high-purity hydrogen gas, the processcomprising:

(1) An organic liquid hydrogen-storage material is contacted and reactedwith a dehydrogenation catalyst to obtain a dehydrogenation reactionproduct containing hydrogen gas;

(2) the dehydrogenation reaction product is cooled to obtain a liquidproduct and a hydrogen-rich gas product, and the liquid product iscollected;

(3) the hydrogen-rich gas is contacted with a hydrogen-storage alloy toobtain a hydrogen-containing alloy, and an unadsorbed gas is collected;

(3a) Optionally, an organic substance in the hydrogen-containing alloystorage container is removed;

(4) The hydrogen-containing alloy is heated to release hydrogen gas,

2. The process for providing high-purity hydrogen gas according to anyof aforementioned.

technical solutions, wherein in step (1):

The reaction temperature for contacting and reacting the organic liquidhydrogen-storage material with the dehydrogenation catalyst is 150 to450° C. (for example, 200 to 400° C., 300 to 350° C.);

The weight hourly space velocity for contacting and reacting the organicliquid hydrogen-storage material with the dehydrogenation catalyst is0.5-50 h⁻¹ (e.g., 1-45 h⁻¹, 2-30 h⁻¹);

The pressure for contacting and reacting the organic liquidhydrogen-storage material with the dehydrogenation catalyst is 3-5 MPa(gauge pressure) (for example 0.3-5 MPa, 0.1-3 MPa, 0.5-2 MPa or 0,2-1,6MPa.);

Optionally, the organic liquid hydrogen-storage material is mixed withhydrogen gas and then contacted with the dehydrogenation catalyst, andthe hydrogen-to-hydrocarbon ratio (the molar ratio of hydrogen gas tothe organic liquid hydrogen-storage material) is 0-10 (for example,0-8):

3. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein in step (2),

The cooling temperature for cooling the dehydrogenation reaction productis lower than the boiling temperature of the organic substance(s) in theliquid product, preferably lower than the boiling temperature of theorganic substance with the lowest boiling point among those being liquidat normal temperature and pressure.

4. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein in step (3).

The hydrogen-rich gas is the hydrogen-rich gas product or ahydrogen-gas-containing gas obtained by further separation of thehydrogen-rich gas product, and the process for the further separationincludes temperature swing separation, membrane separation, pressureswing adsorption separation or a combination thereof.

The mass fraction of hydrogen gas in the hydrogen-rich gas is ≥80% (forexample, 80-99%, preferably ≥85%, more preferably ≥90%).

5. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein in step (3),

Contacting the hydrogen-rich gas with the hydrogen-storage alloy iscarried out in one or more hydrogen-storage alloy storage containers;

The number of the hydrogen-storage alloys) can be one or more, and aplurality of hydrogen-storage alloys can be used in a mixture, or can beused in series or in parallel or in combination of in series and inparallel;

The pressure for contacting the hydrogen-rich gas with thehydrogen-storage alloy is 01-5 MPa (for example, 1-5 MPa, 3-4 MPa, 5-5MPa, 8-2 MPa, 5-3 MPa, 0,1-1 MPa), in case of a plurality ofhydrogen-storage alloy storage containers and in the presence ofhydrogen-storage containers in series, in the hydrogen-rich gas streamdirection, the contact pressure for finally contacting with thehydrogen-storage alloy (also known as the hydrogen absorption pressure)is 5-5 MPa (for example 0.1-1 MPa),

The temperature for contacting the hydrogen-rich gas with thehydrogen-storage alloy (also known as hydrogen absorption temperature)is −70 to 100° C. (for example, −50 to 90° C, −30 to 80° C.);

In case of contacting with the hydrogen-storage alloy, the temperatureof the hydrogen-rich gas is lower than the boiling temperature of theorganic liquid hydrogen-storage material under normal pressure.

6. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein in step (3),

The number of the hydrogen-storage alloy storage container(s) is one ormore, wherein according to the order of contacting with hydrogen gas,the hydrogen-storage alloy in the hydrogen-storage alloy storagecontainer finally contacting with hydrogen gas is a hydrogen-storagealloy having a high equilibrium pressure, wherein the hydrogen-storagealloy having a high equilibrium pressure is such one that there is atleast one temperature point between 150 and 450° C., and at thistemperature point the equilibrium pressure for absorbing hydrogen gas is35 MPa or higher; preferably the hydrogen-storage alloy in at least onehydrogen-storage alloy storage container is a hydrogen-storage alloyhaving a high equilibrium pressure.

7. The process for providing high-purity hydrogen gas according to anyof aforementioned. technical solutions, wherein Step (3a) is performed,wherein the organic substance in the hydrogen-containing alloy storagecontainer is removed by a purge process (for example the purge isperformed with hydrogen gas, for example the process is as follows:after the hydrogen-storage alloy reaches a predetermined adsorptioncapacity, the supply of a hydrogen-rich gas to the hydrogen-storagealloy is stopped, a hydrogen gas is passed through thehydrogen-containing alloy, the organic gas in the hydrogen-containingalloy and in the hydrogen-containing alloy storage container (also knownas hydrogen-storage alloy storage container) is taken out, andintroduced into a storage tank for storage or absorbed by thehydrogen-storage alloy in other hydrogen-storage alloy storagecontainers; wherein preferably, the purity of the hydrogen gas for purgeis greater than 90 wt %, more preferably greater than 95 wt %, forexample greater than 99 wt %).

8. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein in step (4):

The temperature of hydrogen gas released by the hydrogen-storage alloy(namely, the temperature at which the hydrogen-storage alloy is heated,abbreviated as hydrogen release temperature) is 150 to 450° C., thepressure of the released hydrogen gas is ≥35 MPa (for example 35-100MPa) in order to obtain a high-purity and high-pressure hydrogen, or thepartial pressure of the released hydrogen gas is 0.1-5 MPa in order toobtain a high purity hydrogen gas, wherein the hydrogen releasetemperature is higher than the hydrogen absorption temperature.

9. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein the process furthercomprises the hydrogen-containing alloy is allowed to release hydrogengas, and the released hydrogen contacts with different hydrogen-storagealloy(s) to form hydrogen-containing alloy(s), and this process isrepeated once or multiple times, wherein the hydrogen-storage alloy usedin at least the last repetition process is a hydrogen-storage alloyhaving a high equilibrium pressure.

10. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein

The hydrogen-storage alloy is a combination of a first hydrogen-storagealloy and a second hydrogen-storage alloy;

The first hydrogen-storage alloy is a magnesium-based A₂B typehydrogen-storage alloy for contacting with the hydrogen-rich gas,

The second hydrogen-storage alloy is used to pressurize a firsthydrogen-storage hydrogen gas, and the second hydrogen-storage alloy isa hydrogen-storage alloy having a high equilibrium pressure, and thesecond hydrogen-storage alloy is one or more of rare earth-based AB₅type, zirconium-titanium-based AB₂ type, and titanium-based AB typehydrogen-storage alloys;

The hydrogen-rich gas is firstly passed through the firsthydrogen-storage alloy for impurity separation; then the high-purityhydrogen gas released from the first hydrogen-storage alloy is contactedwith the second hydrogen-storage alloy, and then the secondhydrogen-storage alloy is allowed to release hydrogen gas under highpressure.

The hydrogen release temperature of the first hydrogen-storage alloy ishigher than the hydrogen absorption temperature of the secondhydrogen-storage alloy, and the temperature difference is preferably≥100° C. (for example, 350° C. ≥temperature difference ≥150° C.);

The first hydrogen-storage alloy and the second hydrogen-storage alloyare in different hydrogen-storage alloy storage tanks, and there is aheat exchange system between the first hydrogen-storage alloy storagetank and the second hydrogen-storage alloy storage tank;

The hydrogen absorption temperature for contacting the hydrogen-rich gaswith the first hydrogen-storage alloy is 20-150° C. (for example,50-100° C.), and the hydrogen partial pressure is 01-0.1 MPa (01-3 MPa),

The temperature at which the first hydrogen-storage alloy releaseshydrogen gas (hydrogen release temperature) is 150-450° C. (for example,200-350° C.), and the hydrogen gas partial pressure for hydrogen releaseis 0.1-5 MPa (for example, 0.1-1 MPa);

The hydrogen absorption temperature at which the second hydrogen-storagealloy absorbs hydrogen gas is −70 to 100° C. (for example, −30 to 100°C.), and the hydrogen gas partial pressure for hydrogen absorption is0.1-5 MPa (for example, 0.1-1 MPa),

The hydrogen release temperature of the second hydrogen-storage alloy is150-450° C. (for example, 200-350° C.), and the hydrogen gas partialpressure for hydrogen release is 35MPa (for example, 35-100 MPa).

11. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein

The organic liquid hydrogen-storage material. is an organic compoundcontaining a ring in the molecule; which optionally containsheteroatom(s), and the heteroatom(s) may be on the ring; For example,saturated or unsaturated hydrocarbons containing cycloalkane ring(s),for example, saturated or unsaturated hydrocarbons containing noheterocyclic atom and containing cycloalkane ring(s), more specifically,saturated or unsaturated hydrocarbons containing no heterocyclic atomand containing cycloalkane ring(s) and having the total ring number ofaromatic rings and cycloalkanes of 2 or less, for example, cyclohexane,methyl cyclohexane, decahydronaphthalene, and bi(cyclohexane); andsaturated or unsaturated hydrocarbons containing heteroatom(s) andcontaining cycloalkane ring(s), for example, nitrogen-containingheterocyclic compounds, and nitrogen/boron-containing heterocycliccompounds, the nitrogen-containing heterocyclic compound comprises oneor more of decahydrocarbazole, dodecahydroethylcarbazole, indoline,4-aminopiperidine, piperidine-4-carboxamide,perhydro-4,7-phenanthroline, 2-methyl-1,2,3,4-tetrahydroquinoline, and2,6-dimethyldecahydro-1,5-naphthyridine; the nitrogen/boron-containingheterocyclic compound comprises: one or more of 1,2-azaborinane, and3-methyl-1,2-azaborolidine.

12. The process for providing high-purity hydrogen gas according to anyof aforementioned technical solutions, wherein

The process further comprises the released hydrogen gas is introducedinto a hydrogen gas storage tank to store hydrogen gas; or the obtainedhigh-purity and high-pressure hydrogen gas can be directly used torefuel a hydrogen fuel cell vehicle.

13. A high-efficiently distributed process for producing high-purity andhigh-pressure hydrogen gas, the process comprising:

In a dehydrogenation reactor, a liquid organic hydrogen-storage materialis subjected to dehydrogenation reaction in the presence of adehydrogenation catalyst to obtain a dehydrogenation reaction productincluding hydrogen gas;

In a cooling separation apparatus, the dehydrogenation reaction productis cooled and separated to obtain a hydrogen-rich stream and an organicliquid;

In a hydrogen-storage alloy storage container, a hydrogen-rich stream ora purified hydrogen-rich stream is contacted with the hydrogen-storagealloy to obtain a hydrogen-containing alloy;

Purging with hydrogen gas removes an organic substance in thehydrogen-storage alloy storage container; wherein the purity of thehydrogen gas for purge is preferably greater than 90 wt % (for example,greater than 95 wt %, greater than 99 wt %);

The hydrogen-containing alloy is heated to release hydrogen gas toobtain a high-pressure hydrogen gas and supply the obtainedhigh-pressure hydrogen gas to a hydrogen-consuming apparatus or ahigh-pressure hydrogen gas storage tank for storage.

14. A system for providing a high-purity and high-pressure hydrogen gas,comprising:

An organic liquid hydrogen-storage material storage and supplyapparatus, used to store an organic liquid hydrogen-storage material andprovide the organic liquid hydrogen-storage material to adehydrogenation reactor;

A dehydrogenated liquid storage apparatus, used to store the liquidproduct obtained after the dehydrogenation of the organic liquidhydrogen-storage material;

A dehydrogenation reactor apparatus, used for the dehydrogenationreaction of the organic liquid hydrogen-storage material under theaction of the dehydrogenation catalyst to obtain a dehydrogenationreaction product including hydrogen gas;

A cooling separation apparatus, used to separate the dehydrogenationreaction product to obtain a hydrogen-rich gas product and a liquidproduct;

A hydrogen-storage & hydrogen-supply apparatus, which includes ahydrogen-storage alloy storage container and a hydrogen-storage alloyheating system, used to contact the hydrogen-rich gas with thehydrogen-storage alloy to adsorb hydrogen gas at low temperature and lowpressure, and heat to dehydrogenate after the adsorption is saturated;

Optionally, a purge apparatus, used to remove organic substance(s) inthe hydrogen-storage container;

A hydrogen gas supply apparatus, supplying a high-pressure hydrogen tothe hydrogen-consuming apparatus or the hydrogen gas storage tank;

Preferably, the system is configured to be integrated and built in acargo container, and used as a cargo container-type hydrogen productionsystem in a hydrogen refueling station, or directly built in a hydrogenrefueling station for use;

Preferably, the hydrogen-storage & hydrogen-supply apparatus comprisesone or more hydrogen-storage alloy storage containers, a plurality ofhydrogen-storage alloy storage containers can he connected in parallelor in series or in combination of in series and in parallel;

Preferably, at least one of the hydrogen-storage alloy storagecontainers is a high-pressure-resistant container and/or the hydrogengas supply apparatus is a high-pressure-resistant apparatus, forexample, its tolerance pressure is 35 MPa or more.

15. A mobile hydrogen supply system, comprising a transportation vehicleand a system for providing a high-purity and high-pressure hydrogen gasaccording to any of aforementioned technical solutions arranged on thetransportation vehicle.

16. A distributed hydrogen supply apparatus, comprising a system forproviding a high-purity and high-pressure hydrogen according to any ofaforementioned technical solutions, and optionally comprising ahigh-pressure hydrogen gas storage tank.

17. A hydrogen-storage alloy or the process, system or apparatusaccording to any of aforementioned technical solutions, wherein thehydrogen-storage alloy is one or more of rare earth-based AB₅ type,zirconium-titanium-based AB₂ type, titanium-based AB type,magnesium-based A₂B type and vanadium-based solid solution typehydrogen-storage alloys, wherein

The molecular formula of the rare earth-based AB₅ type hydrogen-storagealloy is: M_(m)Ni_(x1)Co_(x2)Mn_(x3)Fe_(x4)Al_(x5)Sn_(x6),4.5≤x1+x2+x3+x4+x5+x6≤0.05.5, wherein, M_(m) isLa_(y1)Ce_(y2)Nd_(y3)Pr_(y4)Y_(y5), y1+y2+y3+y4+y5=1, wherein,0.4≤y1≤0.99 (e.g., 0.4≤y1≤0.8), 0≤y2≤0.45 (e.g., 0.1≤y2≤0.45), 0≤y3≤0.2(e.g., 0≤y3≤0.2), 0≤y4≤0.05 (e.g., 0≤0≤y4≤0.05), 1≤y5≤0.1 (e.g.,1≤y5≤0.05), 3≤x1≤0.05 (e.g., 3≤x1≤4.9), 0≤x2≤1.5 (e.g., 0.1≤x2≤1),0≤x3≤0.8 (e.g., 0.1≤x3≤0.6), 0≤x4≤0.8 (e.g., 0.1≤x4≤0.6), 0≤x5≤0.75(e.g., 0.05≤x5≤0.5), 0≤x6≤0.2; (e.g., 0≤x6≤0.15);

The molecular formula of the zirconium-titanium-based AB₂ typehydrogen-storage alloy is AB₂, whereinA=Mg_(x1)Ca_(x2)Ti_(x3)Zr_(x4)Y_(x5)La_(x6), x1+x2+x3+x4+x5+x6=0.9-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=1.9-2.1, 0≤x1≤0.54 (e.g., 1≤x1≤0.3, 1≤x1≤0.1),0≤x2≤0.54 (e.g., 0≤x2≤0.25), 0.5≤x3≤1.04 (e.g., 0.6≤x3≤1), 5≤x4≤0.58(e.g., 0.1≤x4≤0.58), 1≤x5≤0.2 (e.g., 1≤x5≤0.05), 0≤x6≤0.2 (e.g.,0≤x6≤0.05), 5≤y1≤1.95 (e.g., 5≤y1≤1.8), 0≤y2≤1.9 (e.g., 0≤y2≤1.85),0.05≤y3≤1.95 (e.g., 0.1≤y3≤1.95), 0≤y4≤1.6 (e.g., 0≤y4≤1.5), 0≤y5≤0.5(e.g., 0≤y5≤0.3), 0.1≤y6≤0.5 (e.g., 0.1≤y6≤0.3), 0≤y7≤0.5 (e.g.,0.1≤y7≤0.2), preferably, 0.7≤x3:(x3+x4)≤0.95, preferably,1.7≤y1+y2+y3+y4≤2;

The molecular formula of the titanium-based AB type hydrogen-storagealloy is AB, wherein A=Ti_(x1)Zr_(x2)Y_(x3)La_(x4),x1+x2+x3+x4=0.85-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=0.95-1.05, 0≤x1≤1.09 (e.g., 0.9≤x1≤0.05), 0≤x2≤1.09(e.g., 0≤x2≤0.5), 1≤x3≤0.2 (e.g., 1≤x3≤0.05), 0≤x4≤0.2 (e.g.,0≤x4≤0.05), 0.05≤y1≤0.5 (e.g., 5≤y1≤0.2), 0≤y2≤0.8 (e.g., 0≤y2≤0.2),0≤y3≤0.8 (e.g., 0.05≤y3≤0.4, or 0.1≤y3≤0.4), 0.2≤y4≤1 (e.g.,0.5≤y4≤0.9), 0≤y5≤0.35 (e.g., 0≤y5≤1), 0≤y6≤0.45 (e.g., 0≤y6≤0.2),0≤y7≤0.3 (e.g., 0≤y7≤0.2), preferably, x1 and x2 are zero at the sametime;

The molecular formula of the magnesium-based A₂B type hydrogen-storagealloy is A₂B, wherein A=Mg_(x1)Ca_(x2)Ti_(x3)La_(x4)Y_(x5), x1+x2+x3 +x4+x5=1.9-2.1, B=Cr_(y1)Fe_(y2)Co_(y3)Ni_(y4)Cu_(y5)Mo_(y6);y1+y2+y3+y4+y5+y6=0.9-1.1; wherein, 1.29≤x1≤2.09 (e.g., 1.7≤x1 ≤2.05),0≤x2≤0.5 (e.g., 0≤x2≤0.2), 0≤x3≤0.8 (e.g., 0≤x3≤0.5), 0≤x4≤0.5 (e.g.,0≤x4≤0.2), 1≤x5≤0.2 (e.g., 5≤x5≤0.1), 0≤y1≤0.3 (e.g., 0≤y1≤0.2,5≤y1≤0.2), 0≤y2≤0.2 (e.g., 0≤y2≤0.1), 0≤y3≤0.6 (e.g., 0≤y3≤0.5),02.≤y4≤1.1 (e.g., 0.7≤y4≤0.05), 0≤y5≤0.5 (e.g., 0≤y5≤0.4), 0≤y6≤0.15(e., 0≤y6≤0.1);

The molecular formula of the vanadium-based solid solution typehydrogen-storage alloy is A_(x1)B_(x2), wherein x1+x2=1, whereinA=Ti_(y1)V_(y2)Zr_(y3)Nb_(y4)Y_(y5)La_(y6)Ca_(y7),y1+y2+y3+y4+y5+y6+y7=1, B=Mn_(z1)Fe_(z2)Co_(z3)Ni_(z4), z1+z2+z3+z4=1,0.7≤x1≤0.95 (e.g., 0.8≤x1 ≤0.95, 0.9≤x1≤0.95), 0.05≤x2≤0.3 (e.g.,5≤x2≤0.2, 0.05≤x2≤0.1), 0.40≤y1≤0.9 (e.g., 0.45≤y1≤0.9, 0.5≤y1≤0.8),0≤y2≤0.5 (e.g., 0≤y2≤0.4), 0≤y3≤0.5 (e.g., 0≤y3≤0.4), 0≤y4≤0.55 (e.g.,0≤y4≤0.4), 0≤y5≤0.2 (e.g., 1≤y5≤0.2, 5≤y5≤0.2), 0≤y6≤0.1 (e.g.,0≤y6≤0.05), 0≤y7≤0.1 (e.g., 0≤y7≤5), 0≤z1≤1 (e.g., 0.1≤z1≤1,0.2≤z1≤0.95), 0≤z2≤0.95 (e.g., 0≤z2≤0.9), 0≤z3≤0.3 (e. 0≤z3≤0.2),0≤z4≤0.45 (e.g., 5≤z4≤0.45, 5≤z4≤0.3), 0.55≤z1+z2≤1 (e.g., 0.7≤z1+z2≤1).

18. The hydrogen-storage alloy, process, system or apparatus accordingto any of aforementioned technical solutions, wherein thehydrogen-storage alloy is selected from: La_(0.61)Ce_(0.16)Pr₄Nd_(0.19)Ni_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3),(Ti_(0.8)V_(0.2))_(0.95)(Fe₁)_(0.05),(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.95))_(0.1),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn₁)_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Co_(0.1))_(0.07),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07),(Ti_(0.4)V_(0.4)Zr_(0.2))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Co_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.8)(Mn_(0.7)Ni_(0.3))_(0.2),Ti_(0.64)Zr0.45Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1),Ti_(0.55)Zr_(0.48)Y_(0.05)La_(0.02)V_(0.33)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1),Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1),Ti_(0.6)Zr_(0.4)Y_(0.05)V_(0.1)Mn_(1.8)Ni_(0.2),Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2),Ca_(0.01)Ti_(0.9)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.3),Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05) ¹V_(1.2)Mn_(0.6)Ni_(0.1)Cu_(0.2),TiZr_(0.05)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.3),Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2),Ti_(0.5)Zr_(0.55)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.2),Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1)Cu_(0.1),Mg_(0.01)Ti_(0.63)Zr_(0.45)Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(1.8)Y_(0.1)Ni₁, Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁,Mg_(1.5)Ti_(0.5)Y_(0.05)Ni_(1.1), Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁,Mg₂Y_(0.1)Ni_(0.6)Cu_(0.4), Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4),Mg_(1.92)Y_(0.08)Ni_(0.95)Fe_(0.05),Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05),Mg_(1.9)Y_(0.1)Fe_(0.1)Ni_(0.8)Cu_(0.1),Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1),Mg_(1.9)Y_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.9)Y_(0.1)Cr_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.8)Y_(0.1)La_(0.1)Ni_(0.9)Co_(0.1), Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1),Mg_(1.7)Ti_(0.2)Y_(0.1)Ni_(0.7)Co_(0.32),Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3),TiY_(0.01)V_(0.1)Fe_(0.7)Ni_(0.2),TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1), TiY_(0.02)V_(0.2)Fe_(0.8),TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1),Ti_(0.97)Y_(0.02)V_(0.05)Cr_(0.03)Fe_(0.9),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4),Ti_(0.91)Y_(0.04)V_(0.15)Fe_(0.9),Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.7),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1),Ti_(0.95)Y_(0.05)V_(0.26)Fe_(0.7)Cu_(0.05), Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.9)Ni_(0.1),ATi_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.05),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.6),La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5),La_(0.8)Ce_(0.15)Y_(0.05)Ni_(4.5)Mn_(0.5),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni_(4.2)Co_(0.8),La_(0.75)Ce_(0.5)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2),La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.8)Fe_(0.2),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.4)Mn_(0.1),La_(0.97)Y_(0.03)Ni₄Co₁.

19. The hydrogen-storage alloy, process, system or apparatus accordingto any of aforementioned technical solutions, wherein thehydrogen-storage alloy is selected from:(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1),(T_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07),(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05),Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1),Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1),Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2),Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.1)Cu_(0.2),Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2),Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1)Cu_(0.1),Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁, Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁,Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4),Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05),Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1),Mg_(1.9)Y_(0.1)Cr_(0.1)Ni_(0.8)Co_(0.2),Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1),Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3),TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1),TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4),Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1), Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.55)Al_(0.05),La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2),La_(0.75)Ce_(0.15)N d_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2),La_(0.8)Ce_(0.15)N d_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1).

20. The hydrogen-storage alloy, process, system, or apparatus accordingto any of aforementioned technical solutions, wherein thehydrogen-storage alloy is prepared by the following process, wherein theprocess comprises the following steps:

(1) weighing each of the raw materials of the hydrogen-storage alloy ina way to reach the composition of the hydrogen-storage alloy and mixingthe raw materials;

(2) melting the mixture obtained in step (1) and then annealing;

wherein the melting is electric furnace melting or induction melting;

Preferably, the melting condition comprises: it is performed undervacuum or inert atmosphere, the temperature is 1200-3000° C., preferably1800-2200° C.;

More preferably, it is performed under vacuum, and the melting pressureis 1*10⁻⁵ to 1*10⁻³ Pa (absolute pressure), preferably 0.5*10⁻⁴ to5*10⁻⁴ Pa (absolute pressure);

More preferably, it is performed under inert atmosphere, and the meltingpressure is 0.5-1 bar (for example, 0.6-1 bar, 0.7-1 bar) (gaugepressure),

Wherein the annealing condition comprises: it is performed under vacuumor inert atmosphere (e.g., argon atmosphere), the temperature is5500-900° C. (for example 700-1000° C.), the time is 12-360 hours;Optionally, the process further comprises cooling the material obtainedby annealing in step (2) and then performing a crushing treatment toobtain a product of 10-400 mesh (for example, 20-400 mesh),

Optionally, the process further comprises subjecting the materialobtained by annealing in step (2) to activation treatment; preferably,the condition of the activation treatment comprises: it is performedunder vacuum, the temperature is 50-300° C., and the time is 1-10 hours.

21. A support composition for dehydrogenation catalyst of an organicsubstance, wherein the support composition comprises alumina and amodified metal oxide, and the modified metal oxide is titanium oxideand/or zirconium oxide, wherein, η=0.3, preferably, η=0; θ≥5,preferably, θ is 5-40 (for example, 5.4-34.3);

η=the content by weight percent of the crystal phase of the modifiedmetal oxide in the support composition/the content by weight percent ofthe chemical composition of the modified metal oxide in the supportcomposition,

θ=the content by weight percent of the modified metal oxide on thesurface of the support composition/the content by weight percent of thechemical composition of the modified metal oxide in the supportcomposition, titanium oxide is calculated as TiO₂, zirconium oxide iscalculated as ZrO₂.

22. The support composition for a dehydrogenation catalyst of an organicsubstance according to any of aforementioned technical solutions,wherein the mass fraction of alumina in the support composition is80-98.5% (for example 83-97.5%, 85-95% or 90-95%), the mass fraction ofthe modified metal oxide is 1.5-20% (for example 2.5-17%, 5-15%, or5-10%).

23. The support composition for a dehydrogenation catalyst of an organicsubstance according to any of aforementioned technical solutions,wherein the modified metal oxide comprises titanium oxide; in thesupport composition, the mass fraction of titanium oxide is 2-20% (forexample, 2.5-17%, 5-15% or 5-10%), the mass fraction of zirconiumdioxide is 0-8% (for example, 0-6%, 0-3% or 1-6%); preferably, themodified metal oxide (for example, titanium oxide) in a monolayer isdispersed on the alumina substrate.

24. The support composition for a dehydrogenation catalyst of an organicsubstance according to any of aforementioned technical solutions,wherein relative to the pure phase of TiO₂, in the XPS spectrum of thesupport composition, a peak at the Ti 2P_(3/2) orbital electron bindingenergy of 458.8 eV is shifted by 0.6-0.7 eV to a higher binding energyand/or a peak at the Ti 2P1/2 orbital electron binding energy of 464.5eV is shifted by 0.8-0.9 eV to a higher binding energy.

25. The support composition for a dehydrogenation catalyst of an organicsubstance according to any of aforementioned technical solutions,wherein the support composition has the phase structure of at least oneof γ-alumina, η-alumina, ρ-alumina or χ-alumina.

26. The support composition for a dehydrogenation catalyst of an organicsubstance according to any of aforementioned technical solutions,wherein the support composition has a specific surface area of 100-350m²/g, the support composition has a pore volume of 0.3-1.3 mL/g.

27. A process for preparing a support composition for a dehydrogenationcatalyst of an organic substance according to any of aforementionedtechnical solutions, comprising the following steps:

(1) contacting an alumina substrate with a gas flow of a modified metaloxide precusor carried by a gas to obtain an alumina substrate loadedwith the modified metal oxide precusor, and the modified metal oxideprecusor is titanium oxide precusor and/or zirconium oxide precusor;

(2) Hydrolyzing and calcining the alumina substrate loaded with themodified metal oxide precusor to obtain a support composition.

28. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the titanium oxideprecusor is selected from titanium tetrachloride, (tetra)ethyl titanate,(tetra)butyl titanate, (tetra)isopropyl titanate, titanium acetate, anda mixture thereof (preferably titanium tetrachloride); the zirconiumoxide precusor is selected from zirconium tetrachloride, zirconiumethoxi de, zirconium methoxi de, zirconium isopropoxide, tetrabutylzirconate, and a mixture thereof (preferably zirconium tetrachlorideand/or zirconium methoxide).

29. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the alumina substrate isselected from γ-alumina, η-alumina. ρ-alumina, χ-alumina, hydratedalumina, and a mixture thereof

30. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the alumina substrate hasa specific surface area of 100-350 m²/g; preferably, the ratio of thespecific surface area of the support composition to the specific surfacearea of the alumina substrate is not lower than 90%.

31. The process for preparing the support composition according to anyof aforementioned.

technical solutions, wherein the alumina substrate has a pore volume of0.3-1.3 mL/g.

32. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the gas is an anhydrousinactive gas (for example, nitrogen gas, helium gas, neon gas, argongas), the content of water in the anhydrous inactive gas is not morethan 10 ppm; preferably, the content of the modified metal oxideprecusor in the gas flow of a modified metal oxide precusor carried by agas is 0.1-3 g/L (for example, 0.2-2 g/L), wherein the content of themodified metal oxide precusor is calculated as metal oxide.

33. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein in step (1), thetemperature of the gas is room temperature to 350° C. (for example, roomtemperature (room temperature refers to 15-40° C.) to 300° C., or 15 to300° C.).

34. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the pressure forcontacting in step (1) is 5-5 atm (for example, 1-3 atm) (gaugepressure).

35. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein the ratio of thevolumetric flow rate of the gas per minute to the volume of aluminasubstrate is 3-80:1 (e.g., 5-30:1, 10-25:1); wherein the volume of thegas is calculated as the volume under normal conditions; the volume ofthe alumina substrate is calculated as the bulk volume.

36. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein when the aluminasubstrate is contacted with the gas flow of a. modified metal oxideprecusor carried by a gas, the alumina substrate is in fluidized stateor under stirring; wherein being in fluidized state may be, for example,in a bubbling bed, a turbulent bed, a fast bed or a conveying bed.

37. The process for preparing the support composition according to anyof aforementioned. technical solutions, wherein in step (2), hydrolyzingthe alumina substrate loaded with the modified metal oxide precusor isperformed as follows: the alumina substrate loaded with the modifiedmetal oxide precusor is contacted with a gas containing water vapor. 38.The process for preparing the support composition according to any ofaforementioned technical solutions, wherein for the hydrolysis in step(2), the ratio of the gas containing water vapor to the aluminasubstrate contacted therewith (the ratio of the volume of the gascontaining water vapor and the bulk volume of the alumina substrateunder normal conditions) is 3-80:1 (for example, 5-30:1, or 10-25:1),the proportion of the water vapor in the gas containing water vaporrelative to the total gas volume is 0.1 vol %-100 vol %(for example, 3vol %-100 vol %); other gases) except water vapour in the gas containingwater vapor can be inert gas, nitrogen gas or air. 39. The process forpreparing the support composition according to any of aforementionedtechnical solutions; wherein for the hydrolysis in step (2), thehydrolysis time is 1 hour to 50 hours, for example 2 hours to 30 hours.

40. The process for preparing the support composition according to anyof aforementioned technical solutions, wherein for the calcining, thecalcining temperature is 350° C-700° C., the calcining time is 0.5-12hours (the calcining atmosphere can be an atmosphere not containing theoxygen gas or containing the oxygen gas, in an embodiment, the contentof the oxygen gas in the atmosphere containing the oxygen gas can be3-100 vol %, for example it is an atmosphere of air or an atmosphere ofoxygen gas).

41. A catalyst for producing hydrogen by dehydrogenation of organicsubstance or the hydrogen-storage alloy, process, system or apparatusaccording to any of aforementioned technical solutions, wherein thecatalyst contains the support composition for a dehydrogenation catalystof an organic substance according to any of aforementioned technicalsolutions and an active component.

42. The catalyst for producing hydrogen by dehydrogenation of organicsubstance according to any of aforementioned technical solutions or thehydrogen-storage alloy, process, system or apparatus according to any ofaforementioned technical solutions, wherein the active component is oneof the following (1), (2) and (3):

(1) At least one element in the noble metal group, preferably, theactive component is Pt and optionally at least one element other than Ptin the noble metal group;

(2) Pt and at least one element in the first metal group;

(3) Ni, at least one element in the second metal group, and optionallyphosphorus;

wherein

The noble metal group is a group consisting of elements selected fromPt, Pd, Ru, Re, Rh, Ir, Os;

The first metal group is a group consisting of elements selected fromSn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca;

The second metal group is a group consisting of elements selected fromZn, Sn, Cu, Fe, In, Re, Mo, Co, Ca, and W;

In the catalyst, the content of the support is 70-99.9 wt %; the contentof active component is 0,1-30 wt %.

43. The catalyst for producing hydrogen by dehydrogenation of organicsubstance according to any of aforementioned technical solutions or thehydrogen-storage alloy, process, system or apparatus according to any ofaforementioned technical solutions, wherein the active component is (1)at least one element in the noble metal group, in the catalyst, thecontent of the support is 90-99.9 wt % (for example, 92-99.4 wt %,92-99.5 wt %, 95-99.4 wt %, 98-99.2 wt %, 98.5-99.5 wt %); the contentof active component is 0,1-10 wt % (for example, 0.6-8 wt %, 0.5-8 wt %,0.6-5 wt %, 0.8-2 wt % or 0.5-1.5 wt %); Preferably, the activecomponent is Pt and optionally at least one element other than Pt in thenoble metal group, wherein the content of Pt is 0.1-10 wt % (forexample, 0.1-2 wt %, 0.6-10 wt % or 0.6-0.8 wt %), the content of atleast one element other than Pt in the noble metal group is 0-9.9 wt %(for example, 0.1-2 wt % or 0.1-0.8 wt %).

44. The catalyst for producing hydrogen by dehydrogenation of organicsubstance according to any of aforementioned technical solutions or thehydrogen-storage alloy, process, system or apparatus according to any ofaforementioned technical solutions, wherein the active component is (2)Pt and at least one element in the first metal group;

In the catalyst, the content of the support is 75-99.5 wt % (forexample, 75-99,4 wt %, 79.9-98.5 wt %), the content of active componentis 0.5-25 wt % (for example, 0.6-25 wt %, 1.5-20.1 wt %);

In the active component, the content of Pt (calculated as simplesubstance) is 1-10 wt % (for example, 0.2-8 wt %, 0.4-2 wt %, 0.3-0.6 wt%, 0.1-0.7 wt %); the content of at least one element (calculated asoxide) in the first metal group is 0.5-20 wt % (for example, 0.5-15 wt %or 1-10 wt %); preferably, at least one element in the first metal groupis Ni or is a combination of Ni and at least one element other than Niselected from those in the first metal group, wherein the mass ratio ofPt (calculated as simple substance) to Ni (as NiO) is (0.01:16) to(0.5:0.1).

45. The catalyst for producing hydrogen by dehydrogenation of organicsubstance according to any of aforementioned technical solutions or thehydrogen-storage alloy, process, system or apparatus according to any ofaforementioned technical solutions, wherein the active component is (3)Ni, at least one element in the second metal group, and optionallyphosphorus;

In the catalyst, the content of the support is 70-95 wt % (for example,75-93 wt %, or 75-90 wt %), the content of active component calculatedas oxide is 5-30 wt % (for example, 7-25 wt %);

In the active component, the content of nickel as NiO is 0.5-25 wt %(for example, 5-25 wt %. 6-20 wt %, or 6-11 wt %); the content of atleast one element calculated as oxide in the second.

metal group is 0-15 wt % (for example, 0-10 wt %); the content ofphosphorus as P2O5 is 0-15 wt %.

46. A process for preparing a catalyst, which comprises the followingsteps: steps (1) and (2) in the process for preparing the supportcomposition according to any of aforementioned technical solutions:

(1) contacting an alumina substrate with a gas flow of a modified metaloxide precusor carried by a gas to obtain an alumina substrate loadedwith the modified metal oxide precusor, and the modified metal oxideprecusor is titanium oxide precusor and/or zirconium oxide precusor;

(2) Hydrolyzing and calcining the alumina substrate loaded with themodified metal oxide precusor to obtain a support composition; Whereinthe process for preparing the catalyst further comprises the followingsteps:

(3) Impregnating the support composition with the active componentprecursor solution to obtain a support impregnated with the activecomponent precursor;

(4) Drying and calcining the support impregnated with the activecomponent precursor; Preferably, the active component is one of thefollowing (1), (2) and (3):

(1) At least one element in the noble metal group, preferably, theactive component is Pt and optionally at least one element other than Ptin the noble metal group;

(2) Pt and at least one element in the first metal group;

(3) Ni, at least one element in the second metal group, and optionallyphosphorus;

Wherein

The noble metal group is a group consisting of elements selected fromPt, Pd, Ru, Re, Rh, Ir, and Os;

The first metal group is a group consisting of elements selected fromSn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca;

The second metal group is a group consisting of elements selected fromZn, Sn, In, Re, Mo, Co, Ca, and W.

47. The process for preparing the catalyst according to any ofaforementioned technical solutions, wherein for the calcining in step(4), the calcining temperature is 400-700° C., the calcining time is0.5-12 hours.

48. The process for preparing the catalyst according to any ofaforementioned technical solutions, wherein

The active component precusor is a soluble salt of the active component(for example, one or more of metal nitrate, metal acetate, metalchloride; metal carbonate, metal acetate complex, metal hydroxide, metaloxalate complex, high-valent metal acid, high-valent metal acid salt,metal complex, and ammonium salt).

49. The process for preparing the catalyst according to any ofaforementioned technical solutions, wherein

The support impregnated with the active component precursor is placed inan environment below −40° C. for 1 hour to 24 hours; and then it isvacuum-dried to remove the water adsorbed on the support, and thencalcined to obtain the catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction (XRD) spectrum of a support compositioncontaining alumina and titanium oxide, wherein “1” is an XRD spectrum ofthe support composition (alumina loaded with titanium oxide) provided bythe present invention; “2” is the XRD spectrum of the supportcomposition of alumina loaded with Ti oxide prepared by the impregnationprocess; “3” is the XRD spectrum of the mechanical mixture of aluminaand titanium dioxide, In the XRD curve, the diffraction peaks of TiO₂(anatase) appear at 2θ=25.37°, 48.12°, 53.97°, 55.1°.

FIG. 2 is an X-ray photoelectron spectroscopy (XPS) spectrum, where 1 isthe XPS spectrum of pure TiO₂; the other curves are the XPS spectra ofthe support compositions with different TiO₂ contents (alumina loadedwith titanium oxide) prepared by the process of the present invention,in which M-2, M-4, M-7 and M-8 are the supports of Examples 2, 4, 7 and8 respectively. As can be seen from FIG. 2, for the support compositionprovided by the present invention, a peak at the Ti 2P_(3/2) orbitalelectron binding energy (binding energy) of 458.8 eV is shifted by0.6-0.7 eV to a higher binding energy, and a peak at the Ti 2P1/2orbital electron binding energy of 464.5 eV is shifted by 0.8-0.9 eV toa higher binding energy, indicating that there is an interaction betweenTi and the alumina support.

FIG. 3 is a schematic diagram of providing high-purity and high-pressurehydrogen gas provided by the present invention, in which: 1 is anorganic liquid storage tank, 2 is a material pump, 3 is a heatexchanger, 4 is a dehydrogenation reactor, 5 is a heat exchanger, 6 is ahydrogen-storage tank, 7 is a one-way valve, 8 is an energy transfersystem, 9 is a purge system, and 10 is a hydrogen-storage controlsystem.

DETAILED DESCRIPTION OF THE INVENTION

The pressure in the present invention refers to gauge pressure, unlessotherwise specified. In an aspect of the present invention, the presentinvention provides a support composition for a dehydrogenation catalystof an organic substance, wherein the support composition comprisesalumina and a modified metal oxide, and the modified metal oxide istitanium oxide and/or zirconium oxide, wherein, η=0.3, preferably, η=0;θ≥5, preferably, θ is 5-40 (for example, 5.4-34.3);

η=the content by weight percent of the crystal phase of the modifiedmetal oxide in the support composition/the content by weight percent ofthe chemical composition of the modified metal oxide in the supportcomposition,

θ=the content by weight percent of the modified metal oxide on thesurface of the support composition/the content by weight percent of thechemical composition of the modified. metal oxide in the supportcomposition, titanium oxide is calculated as TiO₂, zirconium oxide iscalculated as ZrO₂.

Preferably, the alumina and the modified metal oxide partly orcompletely form a support composition. In an embodiment, the modifiedmetal oxide is loaded on the surface of the support.

According to the support composition of the present invention, the massfraction of alumina in the support composition is 80-98.5% (for example,83-97.5%, 85-95% or 90-95%), the mass fraction of the modified metaloxide is 1.5-20% (for example, 2.5-17%, 5-15%, or 5-10%).

According to the support composition of the present invention, themodified metal oxide comprises titanium oxide; in the supportcomposition, the mass fraction of titanium oxide is 2-20% (for example,2.5-17%, 5-15% or 5-10%), the mass fraction of zirconium dioxide is 0-8%(for example, 0-6%, 0-3% or 1-6%); preferably, the modified metal oxide(for example, titanium oxide) in a monolayer is dispersed on the aluminasubstrate.

According to an embodiment of the present invention, if measured by XPS,the content of the modified metal oxide in the 0-5nm thick surface layerof the support surface is higher than 90 atomic number %, preferablyhigher than 95 atomic number %, it is called that the modified metaloxide in a monolayer is dispersed on the alumina substrate.

According to the support composition of the present invention, relativeto the pure phase of TiO₂, in the XPS spectrum of the supportcomposition, a peak at the Ti 2P_(3/2) orbital electron binding energyof 458.8 eV is shifted by 0.6-0.7 eV to a higher binding energy and/or apeak at the Ti 2P1/2 orbital electron binding energy of 464.5 eV isshifted by 0.8-0.9 eV to a higher binding energy.

According to the support composition of the present invention, thesupport composition has the phase structure of at least one ofγ-alumina, η-alumina, ρ-alumina or χ-alumina.

According to the support composition of the present invention, thesupport composition has a specific surface area of 100-350 m² /g (forexample, 110-340 m²/g or 130-250 m²/g or 140-200 m²/g), the supportcomposition has a pore volume of 0.3-1.3 mL/g (for example. 0.32-1.0mL/g or 0.35-0.6 mL/g or 0.35-0.8 mL/g). The ratio of the specificsurface area of the support composition to the specific surface area ofthe alumina substrate is not less than 90%, that is, the specificsurface area of the support composition, compared with that of purealumina (alumina without modification by introducing the modifyingelement), is reduced by a proportion of ≤10%.

The support composition provided by the present invention can be used toprepare a catalyst for the dehydrogenation of organic substance toproduce hydrogen gas, and can also be used in a catalyst for theoxidative dehydrogenation of alkane organic substances to prepareolefins or oxygen-containing organic substances. Generally, the catalystincludes the support composition provided by the present invention andthe active metal component loaded on the support composition, and theactive metal component is an oxide of the active metal and/or a

simple substance of the active metal. The active metal is one or more ofgroup metal, VIIB group metal, VB group metal, VIB group metal, IB groupmetal, rare earth element, alkaline earth metal, IRA group metal. Thecatalyst of the present invention can have higher dehydrogenationactivity and/or higher selectivity than catalysts prepared by using theknown support and the same active metal.

The support composition provided by the present invention has arelatively low n value and a relatively high 0 value. It can be used asa dehydrogenation catalyst support, especially used in a catalyst forthe dehydrogenation of a cycloalkane ring-containing organic liquidhydrogen-storage compound to prepare hydrogen gas, and can improve thedehydrogenation activity and/or selectivity of the catalyst.

The preparation process of the support composition provided by thepresent invention can produce the support composition provided by thepresent invention. The produced support composition has a relatively lowη value and a relatively high θ value, and the preparation process iseasy to implement.

The dehydrogenation catalyst prepared with the support compositionprovided by the present invention for producing hydrogen gas bydehydrogenating organic liquid hydrogen-storage compounds has higheractivity and higher hydrogen selectivity. The prepared oxidativedehydrogenation catalyst has higher activity and higher oxidationselectivity.

The support provided by the present invention can be used to prepare acatalyst for producing hydrogen gas by dehydrogenation of organichydrogen-storage compounds, and can also be used as a support for otherhydrogen-related reaction catalysts or oxidation catalysts, for example,for organic substance oxidative dehydrogenation catalysts, unsaturatedhydrocarbon hydrogenation catalysts, organic substance completeoxidation catalyst or NO oxidation catalyst.

In one aspect of the present invention, the present invention provides aprocess for preparing a support composition, comprising the followingsteps: (1) contacting an alumina substrate with a gas flow of a modifiedmetal oxide precusor carried by a gas to obtain an alumina substrateloaded with the modified metal oxide precusor, and the modified metaloxide precusor is titanium oxide precusor and/or zirconium oxideprecusor; (2) Hydrolyzing and calcining the alumina substrate loadedwith the modified metal oxide precusor to obtain a support composition.

According to the preparation process of the support composition of thepresent invention, the modified metal oxide precursor is preferably asubstance that can be vaporized to form a gaseous metal oxide precursorat room temperature to 350° C. The titanium oxide precusor is selectedfrom titanium tetrachloride, (tetra)ethyl titanate, (tetra)butyltitanate, (tetra.)isopropyl titanate, titanium acetate, and a mixturethereof (preferably titanium tetrachloride); the zirconium oxideprecusor is selected from zirconium tetrachloride, zirconium ethoxide,zirconium methoxide, zirconium isopropoxide, tetrabutyl zirconate, and amixture thereof (preferably zirconium tetrachloride and/or zirconiumtnethoxide).

According to the preparation process for the support composition of thepresent invention, the alumina substrate is selected from γ-alumina.η-alumina, ρ-alumina, χ-alumina, hydrated alumina (for example,boehmite, diaspore, pseudo-boehmite, gibbsite, hayerite, nordstrandite,amorphous aluminium hydroxide), and a mixture thereof, preferably, theaverage particle size (diameter) of the alumina substrate) is 5-100 μm,for example 5-50 μm.

According to the preparation process for the support composition of thepresent invention, the alumina substrate has a specific surface area ofnot less than 100 m²/g (for example, more than 100 and not more than 380m²/g, 100-350 m²/g, 125-335 m²/g); Preferably, the ratio of the specificsurface area of the support composition to the specific surface area ofthe alumina substrate is not less than 90%, that is, the specificsurface area of the obtained support composition, compared with that ofthe alumina substrate, is reduced by a proportion of ≤10%.

According to the process for preparing the support composition of thepresent invention, the alumina substrate has a pore volume of not lowerthan 0.3 mL/g (for example, more than 0.3 and not more than 1.45 mL/g,0.3-1.3 mL/g, 0.35-1.2 mL/g, 0.35-1.0 or 0.4-0.8 mL/g).

According to the process for preparing the support composition of thepresent invention, the gas is an anhydrous inactive gas (for example,nitrogen gas, helium gas, neon gas, argon gas), the content of water inthe anhydrous inactive gas is not more than 10 ppm; preferably, thecontent of the modified metal oxide precusor in the gas flow of amodified metal oxide precusor carried by a gas is 0.1-3 g/I: (forexample, 0.2-2 g/L), wherein the content of the modified metal oxideprecusor is calculated as metal oxide.

According to the process for preparing the support composition of thepresent invention, in step (1), the temperature of the gas is roomtemperature to 350° C. (for example, room Temperature (room temperaturerefers to 15-40° C.) to 300° C., or 15 to 300° C.), the temperature forcontacting is 15-350° C. (for example, 15-300° C. or 15-100° C. or15-200° C. or 18-60° C. or 15-40° C.).

According to the process for preparing the support composition of thepresent invention, the pressure for contacting in step (1) is 0.5-5 atm(for example, 1-3 atm) (gauge pressure).

According to the process for preparing the support composition of thepresent invention, the ratio of the volumetric flow rate of the gas perminute to the volume of alumina substrate is 3-80:1 (e.g., 5-30:1,10-25:1); wherein the volume of the gas is calculated as the volumeunder normal conditions, the volume of the alumina substrate iscalculated as the bulk volume.

According to the process for preparing the support composition of thepresent invention, when the alumina substrate is contacted with the gasflow of a modified metal oxide precusor carried by a gas, the aluminasubstrate is in fluidized state or under stirring; wherein being influidized state may be, for example, in a bubbling bed, a turbulent bed,a fast bed or a conveying bed.

In an embodiment, the alumina substrate is contacted with a gas flow ofa modified metal oxide precusor carried by a gas (also known as gasflow), the alumina substrate is contacted. in a fixed bed with the gasflow, or is contacted in the fluidized state with the gas flow of amodified metal oxide precusor carried by a gas; or can be contactedunder stirring with the gas flow. The contacting in fluidized state maybe for example the contacting in a bubbling bed, a turbulent bed; a fastbed or a conveying bed. The ratio of the volumetric flow rate of the gasper minute to the volume of the alumina substrate is 3-80:1, for example5-30:1, or 10-25:1, wherein the volume of the gas is calculated as thevolume under normal conditions; and the volume of the alumina substrateis calculated as the bulk volume. In another embodiment, the gas flow iscontacted with the alumina substrate in a fluidized bed, and thevolumetric space velocity for the contacting is 3-80:1 min⁻¹, forexample 5-30:1 min⁻¹or 10-25:1 min⁻¹, wherein the volumetric flow rateof the gas flow is based on the volume of the gas under normalconditions, the alumina substrate is calculated as the bulk volume, andthe fluidized bed can be a bulk fluidized bed, a bubbling bed or aturbulent bed.

According to the process for preparing the support composition of thepresent invention, in step (2), hydrolyzing the alumina substrate loadedwith the modified metal oxide precusor is performed as follows: thealumina substrate loaded with the modified metal oxide precusor iscontacted with a gas containing water vapor.

According to the process for preparing the support composition of thepresent invention, for the hydrolysis in step (2), the ratio of the gascontaining water vapor to the alumina substrate contacted therewith (theratio of the volume of the gas containing water vapor and the bulkvolume of the alumina substrate under normal conditions) is 3-80:1 (forexample; 5-30:1, or 10-25:1), the proportion of the water vapor in thegas containing water vapor relative to the total gas volume is 0.1 vol%-100 vol % (for example, 3 vol %-100 vol %, 10 vol %-70 vol %); othergas(es) except water vapour in the gas containing water vapor can beinert gas, nitrogen gas or air.

According to the process for preparing the support composition of thepresent invention, for the hydrolysis in step (2), the hydrolysis timeis 1 hour to 50 hours, for example 2 hours to 3( ) hours (usually, thehydrolysis time is greater than or equal to the loading time; theloading time refers to the time for contacting alumina substrate withthe gas flow of a modified metal oxide precusor carried by a gas).

According to the process for preparing the support composition of thepresent invention, the calcining atmosphere can be an atmosphere notcontaining the oxygen gas or containing the oxygen gas. In anembodiment, the content of the oxygen gas in the atmosphere containingthe oxygen gas can be 3-100 vol %, for example it is an atmosphere ofair or an atmosphere of oxygen gas. The calcining temperature is 350°C-700° C. (e.g., 400-700° C.), the calcining time is 0.5-12 hours (forexample, 1-10 hours, or 2-9 hours, or 4-8 hours).

In an aspect of the present invention, the present invention provides acatalyst for producing hydrogen by dehydrogenation of organic substance,wherein the catalyst contains the support composition for adehydrogenation catalyst of an organic substance according to thepresent invention and an active component.

In the catalyst provided by the present invention, the active componentsmay exist in the form of oxides and/or active metal simple substances.

According to the catalyst for producing hydrogen by dehydrogenation oforganic substance of the present invention, the active component is oneof the following (1), (2) and (3): (1) At least one element in the noblemetal group, preferably, the active component is Pt and optionally atleast one element other than Pt in the noble metal group; (2) Pt and atleast one element in the first metal group; (3) Ni, at least one elementin the second metal group, and optionally phosphorus; wherein The noblemetal group is a group consisting of elements selected from Pt, Pd, Ru.Re, Rh, Ir, and Os; The first metal group is a group consisting ofelements selected from Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu,and Ca; The second metal group is a group consisting of elementsselected from Zn, Sn, Cu, Fe, Ag, In, Re, Mo, Co, Ca, and W; In thecatalyst, the content of the support is 70-99.9 wt %; the content ofactive component is 0.1-30 wt %.

According to the catalyst for producing hydrogen by dehydrogenation oforganic substance of the present invention, the active component is (1)at least one element in the noble metal group, in the catalyst, thecontent of the support is 90-99.9 wt % (for example, 92-99.4 wt %,92-99.5 wt %, 95-99.4 wt %, 98-99.2 wt %, 98.5-99.5 wt %); the contentof active component is 0.1-10 wt % (for example, 0.6-8 wt %, 0.5-8 wt %,0.6-5 wt %, 0.8-2 wt % or 0.5-1,5 wt %); preferably, the activecomponent is Pt and optionally at least one element other than Pt in thenoble metal group, wherein the content of Pt is 0.1-10 wt % (forexample, 0.1-2 wt %, 0.6-10 wt % or 0.6-0.8 wt %), the content of atleast one element other than Pt in the noble metal group is 0-9.9 wt %(for example, 0.1-2 wt % or 0.1-0.8 wt %).

According to the catalyst for producing hydrogen by dehydrogenation oforganic substance of the present invention, the active component is (2)Pt and at least one element in the first metal group (for example, oneor more of Sn, Ni, Mn, and Cu); In the catalyst, the content of thesupport is 75-99.5 wt % (for example, 75-99.4 wt %, 79,9-98.5 wt %), thecontent of active component is 0.5-25 wt % (for example, 0.6-25 wt %,1.5-20.1 wt %); in the active component, the content of Pt (calculatedas simple substance) is 1-10 wt % (for example, 0.2-8 wt %, 0.4-2 wt %,0.3-0.6 wt %, 0.1-0.7 wt %); the content of at least one element(calculated as oxide) in the first metal group is 0.5-20 wt % (forexample, 0.5-15 wt % or 1-10 wt %); preferably, at least one element inthe first metal group is Ni or a combination of Ni and at least oneelement other than Ni selected from those in the first metal group (forexample, Sn, Mn, and Cu, preferably Cu), wherein the mass ratio of Pt(calculated as simple substance) to Ni (as NiO) is (1:16) to (0.5:0.1).Preferably, in the catalyst the content of Pt is 0.1-0.5 wt %, thecontent of Ni as oxide is 0.5-15 wt %, for example 1-10 wt %, thecontent of the element other than Ni (as oxide) in the first metal groupis 0-10 wt %, for example 1-6 wt %. The active component is further morepreferably Pt, Ni and Cu.

According to the catalyst for producing hydrogen by dehydrogenation oforganic substance of the present invention, the active component is (3)Ni, at least one element in the second metal group (preferably, Sn, Cu,Zn, Fe, Ag, more preferably, Sn, Ag, Cu and Zn, further preferably Sn,Zn and Cu, still further preferably Sn and Zn), and optionallyphosphorus, According to this preferred embodiment, it can have higherconversion rate and hydrogen generation rate, and can have higherhydrogen selectivity relative to other active metals. In the catalyst,the content of the support is 70-95 wt % (for example, 75-93 wt %, or75-90 wt %), the content of active component calculated as oxide is 5-30wt % (for example, 7-25 wt %, 10-25 wt %, 8-20 wt %, or 10-16 wt %); inthe active component, the content of nickel as NiO is 0.5-25 wt % (forexample, 0.5-20 wt %, 5-25 wt %, 6-20 wt %, 5-15 wt %, 8-10 wt %, or6-11 wt %), the content of at least one element calculated as oxide inthe second metal group is 0-15 wt % (for example, 0-10 wt %, 2-6 wt %);the content of phosphorus as P205 is 0-15 wt % (for example; 0-8 wt %,0-6 wt %).

According to the catalyst for producing hydrogen by dehydrogenation oforganic substance of the present invention, the specific surface of thecatalyst is 100-350 rn²/g (for example, 120-330 m²/g), the pore volumeof the catalyst is 0.3-1.3 ml/g (for example, 0.35-1.2 ml/g).

In an aspect of the present invention, the present invention provides aprocess for preparing the catalyst for producing hydrogen bydehydrogenation of organic substance of the present invention, whichcomprises the following steps: (1) contacting an alumina substrate witha gas flow of a modified metal oxide precusor carried by a gas to obtainan alumina substrate loaded with the modified metal oxide precusor, andthe modified metal oxide precusor is titanium oxide precusor and/orzirconium oxide precusor; (2) Hydrolyzing and calcining the aluminasubstrate loaded with the modified metal oxide precusor to obtain asupport composition; (3) Impregnating the support composition with theactive component precursor solution to obtain a support impregnated withthe active component precursor; (4) Drying and calcining the supportimpregnated with the active component precursor; Preferably, the activecomponent is one of the following (1), (2) and (3): (1) At least oneelement in the noble metal group, preferably, the active component is Ptand optionally at least one element other than Pt in the noble metalgroup; (2) Pt and at least one element in the first metal group; (3) Ni,at least one element in the second metal group, and optionallyphosphorus; wherein the noble metal group is a group consisting ofelements selected from Pt, Pd, Ru, Re, Rh, Ir, and Os; the first metalgroup is a group consisting of elements selected from Sn, V, Mo, Cr, Mn,Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and. Ca; the second metal group is agroup consisting of elements selected from Zn, Sn, Cu, Fe, Ag, In, Re,Mo, Co, Ca, and W.

According to the process for preparing the catalyst for producinghydrogen by dehydrogenation of organic substance of the presentinvention, for the calcining in step (4), the calcining temperature is400-700° C., the calcining, time is 0.5-12 hours.

In one embodiment, when the support composition is impregnated with thesolution of the active component precursor, it usually includesdissolving the active metal component precursor in water andimpregnating the support composition to obtain a support impregnatedwith the active metal component precursor. The impregnation process canbe an existing impregnation process, for example, it can be an isometricimpregnation process or an excessive impregnation process. The water isone or more of deionized water, distilled water or decationized water.It is also possible to dissolve the metal precursor in water to obtain ametal precursor solution; the metal precursor solution is introducedonto the support by co-impregnation or step-by-step impregnation. Theimpregnation can be saturation impregnation or supersaturationimpregnation. When the catalyst contains two or more than two metalactive elements, the co-impregnation means that two or more than twometal elements can be dissolved in deionized water together, and thenthe impregnation liquor is impregnated onto the support, and then thesupport is dried and calcined. The step-by-step impregnation includesdissolving two or more than two metal elements in deionized water; themetal impregnation liquor is impregnated on the support separately, andthe support obtained after each impregnation needs to be dried andcalcined, and there is no requirement on the order of introducing themetal, For example, the precursor of Pt and the precursor of one elementin the first metal group can be formulated into a solution to impregnatethe support composition, or the impregnation with the precursor of Ptcan be firstly performed followed by drying and then the impregnationwith the precursor of the element in the first metal group. For example,the liquid/solid volume ratio of the impregnation liquor to the supportduring impregnation is 0.3-5.0, preferably 0,6-4.0, and the impregnationtemperature is 10-50° C., preferably 15-40° C. Preferably; theimpregnated support is allowed to stand at room temperature for 2-10hours, and the impregnated support is dried and then calcined, Thecalcining temperature is preferably 400-700

ãC, and the calcining time is preferably 0.5-12 hours, such as 1-10hours or 2-9 hours or 4-8 hours. There is no special requirements to thecalcining atmosphere. For example, the calcining can be performed inair. During the calcining, the volume ratio of air (normal conditions)to the catalyst is, for example, 400-1000:1, and the calcining time ispreferably 4-8 hours. According to the process for preparing thecatalyst for producing hydrogen by dehydrogenation of organic substanceof the present invention, the active component precusor is a solublesalt of the active component (for example, one or more of metal nitrate;metal acetate, metal chloride, metal carbonate, metal acetate complex,metal hydroxide, metal oxalate complex, high-valent metal acid,high-valent metal acid salt, metal complex, and ammonium salt), In oneembodiment, the high-valent metal acid/high-valent metal acid salt is,for example, one or more of chloroplatinic acid, ammoniumchloroplatinate; tetraammineplatinum nitrate, and tetraammineplatinumhydroxide. The precursor of phosphorus is, for example, one or more ofammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogenphosphate, phosphoric acid, and metal phosphate. According to theprocess for preparing the catalyst for producing hydrogen bydehydrogenation of organic substance of the present invention, thesupport impregnated with the active component precursor is placed in anenvironment below −40

ãC for 1 hour to 24 hours; and then it is vacuum-dried to remove thewater adsorbed on the support, and then calcined to obtain the catalyst.

In an aspect of the present invention, the present invention provides ahydrogen-storage alloy, wherein the hydrogen-storage alloy is one ormore of rare earth-based AB₅ type, zirconium-titanium-based AB₂ type,titanium-based AB type, magnesium-based A₂B type and vanadium-basedsolid solution type hydrogen-storage alloys, wherein

The molecular formula of the rare earth-based AB₅ type hydrogen-storagealloy is: M_(m)Ni_(x1)Co_(x2)Mn_(x3)Fe_(x4)Al_(x5)Sn_(x6),4.5≤x1+x2+x3+x4+x5+x6≤0.05.5, wherein, M_(m) isLa_(y1)Ce_(y2)Nd_(y3)Pr_(y4)Y_(y5), y1+y2+y3+y4+y5=1, wherein,0.4≤y1≤0.99 (e.g., 0.4≤y1≤0.8), 0≤y2≤0.45 (e.g., 0.1≤y2≤0.45), 0≤y3≤0.2(e.g., 0≤y3≤0.2), 0≤y4≤0.05 (e.g., 0≤0≤y4≤0.05), 1≤y5≤0.1 (e.g.,1≤y5≤0.05), 3≤x1≤0.05 (e.g., 3≤x1≤4.9), 0≤x2≤1.5 (e.g., 0.1≤x2≤1),0≤x3≤0.8 (e.g., 0.1≤x3≤0.6), 0≤x4≤0.8 (e.g., 0.1≤x4≤0.6), 0≤x5≤0.75(e.g., 5≤x5≤0.5), 0≤x6≤0.2; (e.g., 0≤x6≤0.15);

The molecular formula of the zirconium-titanium-based AB₂ typehydrogen-storage alloy is AB₂, whereinA=Mg_(x1)Ca_(x2)Ti_(x3)Zr_(x4)Y_(x5)La_(x6), x1+x2+x3+x4+x5+x6=0.9-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=1.9-2.1, 0≤x1≤0.54 (e.g., 1≤x1≤0.3, 1≤x1≤0.1),0≤x2≤0.54 (e.g., 0≤x2≤0.25), 0.5≤x3≤1.04 (e.g., 0.6≤x3≤1), 5≤x4≤0.58(e.g., 0.1≤x4≤0.58), 1≤x5≤0.2 (e.g., 1≤x5≤0.05), 0≤x6≤0.2 (e.g.,0≤x6≤0.05), 5≤y1≤1.95 (e.g., 5≤y1≤1.8), 0≤y2≤1.9 (e.g., 0≤y2≤1.85),5≤y3≤1.95 (e.g., 0.1≤y3≤1.95), 0≤y4≤1.6 (e.g., 0≤y4≤1.5), 0≤y5≤0.5(e.g., 0≤y5≤0.3), 0.1≤y6≤0.5 (e.g., 0.1≤y6≤0.3), 0≤y7≤0.5 (e.g.,0.1≤y7≤0.2), preferably, 0.7≤x3:(x3+x4)≤0.95, preferably,1.7≤y1+y2+y3+y4≤2;

The molecular formula of the titanium-based AB type hydrogen-storagealloy is AB, wherein A=Ti_(x1)Zr_(x2)Y_(x3)La_(x4),x1+x2+x3+x4=0.85-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=0.95-1.05, 0≤x1≤1.09 (e.g., 0.9≤x1≤0.05), 0≤x2≤1.09(e.g., 0≤x2≤0.5), 1≤x3≤0.2 (e.g., 1≤x3≤0.05), 0≤x4≤0.2 (e.g.,0≤x4≤0.05), 5≤y1≤0.5 (e.g., 5≤y1≤0.2), 0≤y2≤0.8 (e.g., 0≤y2≤0.2),0≤y3≤0.8 (e.g., 0.05≤y3≤0.4, or 0.1≤y3≤0.4), 0.2≤y4≤1 (e.g.,0.5≤y4≤0.9), 0≤y5≤0.35 (e.g., 0≤y5≤1), 0≤y6≤0.45 (e.g., 0≤y6≤0.2),0≤y7≤0.3 (e.g., 0≤y7≤0.2), preferably, x1 and x2 are zero at the sametime;

The molecular formula of the magnesium-based A₂B type hydrogen-storagealloy is A₂B, wherein A=Mg_(x1)Ca_(x2)Ti_(x3)La_(x4)Y_(x5), x1+x2+x3 +x4+x5=1.9-2.1, B=Cr_(y1)Fe_(y2)Co_(y3)Ni_(y4)Cu_(y5)Mo_(y6);y1+y2+y3+y4+y5+y6=0.9-1.1; wherein, 1.29≤x1≤2.09 (e.g., 1.7≤x1 ≤2.05),0≤x2≤0.5 (e.g., 0≤x2≤0.2), 0≤x3≤0.8 (e.g., 0≤x3≤0.5), 0≤x4≤0.5 (e.g.,0≤x4≤0.2), 1≤x5≤0.2 (e.g. 5≤x5≤0.1), 0≤y1≤0.3 (e.g., 0≤y1≤0.2,0.05≤y1≤0.2), 0≤y2≤0.2 (e.g., 0≤y2≤0.1), 0≤y3≤0.6 (e.g., 0≤y3≤0.5),02.≤y4≤1.1 (e.g., 0.7≤y4≤0.05), 0≤y5≤0.5 (e.g., 0≤y5≤0.4), 0≤y6≤0.15(e., 0≤y6≤0.1);

The molecular formula of the vanadium-based solid solution typehydrogen-storage alloy is A_(x1)B_(x2), wherein x1+x2=1, whereinA=Ti_(y1)V_(y2)Zr_(y3)Nb_(y4)Y_(y5)La_(y6)Ca_(y7),y1+y2+y3+y4+y5+y6+y7=1, B=Mn_(z1)Fe_(z2)Co_(z3)Ni_(z4), z1+z2+z3+z4=1,0.7≤x1≤0.95 (e.g., 0.8≤x1 ≤0.95, 0.9≤x1≤0.95), 0.05≤x2≤0.3 (e.g.,5≤x2≤0.2, 0.05≤x2≤0.1), 0.40≤y1≤0.9 (e.g., 0.45≤y1≤0.9, 0.5≤y1≤0.8),0≤y2≤0.5 (e.g., 0≤y2≤0.4), 0≤y3≤0.5 (e.g., 0≤y3≤0.4), 0≤y4≤0.55 (e.g.,0≤y4≤0.4), 0≤y5≤0.2 (e.g., 1≤y5≤0.2, 0.05≤y5≤0.2), 0≤y6≤0.1 (e.g.,0≤y6≤0.05), 0≤y7≤0.1 (e.g., 0≤y7≤5), 0≤z1≤1 (e.g., 0.1≤z1≤1,0.2≤z1≤0.95), 0≤z2≤0.95 (e.g., 0≤z2≤0.9), 0≤z3≤0.3 (e. 0≤z3≤0.2),0≤z4≤0.45 (e.g., 0.05≤z4≤0.45, 5≤z4≤0.3), 0.55≤z1+z2≤1 (e.g.,0.7≤z1+z2≤1).

In an embodiment, the hydrogen-storage alloy of the present invention isselected from: La_(0.61)Ce_(0.16)Pr₄Nd_(0.19)Ni_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3),(Ti_(0.8)V_(0.2))_(0.95)(Fe₁)_(0.05),(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.95))_(0.1),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn₁)_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Co_(0.1))_(0.07),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07),(Ti_(0.4)V_(0.4)Zr_(0.2))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Co_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.8)(Mn_(0.7)Ni_(0.3))_(0.2),Ti_(0.64)Zr0.45Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1),Ti_(0.55)Zr_(0.48)Y_(0.05)La_(0.02)V_(0.33)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1),Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1),Ti_(0.6)Zr_(0.4)Y_(0.05)V_(0.1)Mn_(1.8)Ni_(0.2),Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2),Ca_(0.01)Ti_(0.9)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.3),Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05) ¹V_(1.2)Mn_(0.6)Ni_(0.1)Cu_(0.2),TiZr_(0.05)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.3),Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2),Ti_(0.5)Zr_(0.55)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.2),Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1)Cu_(0.1),Mg_(0.01)Ti_(0.63)Zr_(0.45)Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(1.8)Y_(0.1)Ni₁, Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁,Mg_(1.5)Ti_(0.5)Y_(0.05)Ni_(1.1), Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁,Mg₂Y_(0.1)Ni_(0.6)Cu_(0.4), Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4),Mg_(1.92)Y_(0.08)Ni_(0.95)Fe_(0.05),Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05),Mg_(1.9)Y_(0.1)Fe_(0.1)Ni_(0.8)Cu_(0.1),Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1),Mg_(1.9)Y_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.9)Y_(0.1)Cr_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.8)Y_(0.1)La_(0.1)Ni_(0.9)Co_(0.1), Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1),Mg_(1.7)Ti_(0.2)Y_(0.1)Ni_(0.7)Co_(0.32),Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3),TiY_(0.01)V_(0.1)Fe_(0.7)Ni_(0.2),TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1), TiY_(0.02)V_(0.2)Fe_(0.8),TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1),Ti_(0.97)Y_(0.02)V_(0.05)Cr_(0.03)Fe_(0.9),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4),Ti_(0.91)Y_(0.04)V_(0.15)Fe_(0.9),Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.7),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1),Ti_(0.95)Y_(0.05)V_(0.26)Fe_(0.7)Cu_(0.05), Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.9)Ni_(0.1),ATi_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.05),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.6),La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5),La_(0.8)Ce_(0.15)Y_(0.05)Ni_(4.5)Mn_(0.5),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni_(4.2)Co_(0.8),La_(0.75)Ce_(0.5)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2),La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.8)Fe_(0.2),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.4)Mn_(0.1),La_(0.97)Y_(0.03)Ni₄Co₁.

In a preferable embodiment, the hydrogen-storage alloy of the presentinvention is selected from:(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1),(T_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07),(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05),Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1),Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1),Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2),Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.1)Cu_(0.2),Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2),Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1)Cu_(0.1),Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁, Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁,Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4),Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05),Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1),Mg_(1.9)Y_(0.1)Cr_(0.1)Ni_(0.8)Co_(0.2),Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1),Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3),TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1),TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4),Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1), Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.55)Al_(0.05),La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2),La_(0.75)Ce_(0.15)N d_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2),La_(0.8)Ce_(0.15)N d_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1).

In an aspect of the present invention, the present invention provides aprocess for preparing the hydrogen-storage alloy of the presentinvention, wherein the process comprises the following steps: (1)weighing each of the raw materials of the hydrogen-storage alloy in away to reach the composition of the hydrogen-storage alloy and mixingthe raw materials; (2) melting the mixture obtained in step (I) and thenannealing; Wherein the melting is electric furnace melting or inductionmelting; Preferably, the melting condition comprises: it is performedunder vacuum or inert atmosphere, the temperature is 1200-3000

ãC, preferably 1800-2200

ãC; More preferably, it is performed under vacuum, and the meltingpressure is 1*1 0⁻⁵ to 1*10³ Pa (absolute pressure), preferably 0.5*10⁻⁴to 5*10⁻⁴ Pa (absolute pressure); More preferably, it is performed underinert atmosphere, and the melting pressure is 0.5-1 bar (for example,0.6-1 bar, 0.7-1 bar) (gauge pressure); Wherein the annealing conditioncomprises: it is performed under vacuum or inert atmosphere (e.g., argonatmosphere), the temperature is 500-900° C. (for example 700-1000° C.),the time is 12-360 hours; Optionally, the process further comprisescooling the material obtained by, annealing in step (2) and thenperforming a crushing treatment to obtain a product of 10-400 mesh (forexample, 20-400 mesh); And optionally, the process further comprisessubjecting the material obtained by annealing in step (2) to activationtreatment; preferably, the condition of the activation treatmentcomprises: it is performed under vacuum, the temperature is 50-300

ãC, and the time is 1-10 hours.

In an aspect of the present invention, the present invention provides aprocess for providing a high-purity hydrogen gas, wherein the processcomprises: (1) An organic liquid hydrogen-storage material is contactedand reacted with a dehydrogenation catalyst to obtain a dehydrogenationreaction product containing hydrogen; (2) the dehydrogenation reactionproduct is cooled to obtain a liquid product and a hydrogen-rich gasproduct, and the liquid product is collected; (3) the hydrogen-rich gasis contacted with a hydrogen-storage alloy to obtain ahydrogen-containing alloy, and an unadsorbed gas is collected; (3a)Optionally, an organic substance in the by alloy storage container isremoved; (4) The hydrogen-containing alloy is heated to release hydrogengas.

According to the process for providing a high-purity hydrogen gas of thepresent invention, the catalyst for producing hydrogen bydehydrogenation of organic substance of the present invention and/or thehydrogen-storage alloy of the present invention are used.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (1): the reaction temperature for contactingand reacting the organic liquid hydrogen-storage material with thedehydrogenation catalyst is 150 to 450° C. (for example, 200 to 400° C.,300 to 350° C.); the weight hourly space velocity for contacting andreacting the organic liquid hydrogen-storage material with thedehydrogenation catalyst is 0.5-50 h⁻¹ (e.g., 1-45 h⁻¹, 2-30 h⁻¹); thepressure for contacting and reacting the organic liquid hydrogen-storagematerial with the dehydrogenation catalyst is 0.03-5 MPa (gaugepressure) (for example, 0.3-5 MPa, 0.1-3 MPa, 0.5-2 MPa or 0.2-1.6 MPa);Optionally, the organic liquid hydrogen-storage material is mixed withhydrogen gas and then contacted with the dehydrogenation catalyst, andthe hydrogen-to-hydrocarbon ratio (the molar ratio of hydrogen gas tothe organic liquid hydrogen-storage material) is 0-10 (for example,0-8). The introduction of hydrogen gas is beneficial to reduce cokeformation in the dehydrogenation reaction.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (2), the cooling temperature for cooling thedehydrogenation reaction product is lower than the boiling temperatureof the organic substance(s) in the liquid product; preferably lower thanthe boiling temperature of the organic substance with the lowest boilingpoint among those being liquid at normal temperature and pressure.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (3), the hydrogen-rich gas is thehydrogen-rich gas product or a hydrogen-containing gas obtained byfurther separation of the hydrogen-rich gas product, the process for thefurther separation includes temperature swing separation; membraneseparation, pressure swing adsorption separation or a combinationthereof; The mass fraction of hydrogen gas in the hydrogen-rich gas is≥80% (for example, 80-99%, preferably ≥85%, more preferably ≥90%). Thehydrogen-rich gas with a certain content of hydrogen gas obtained bycooling and separating is then subjected to the absorption with thehydrogen-storage alloy, the absorption capacity of the hydrogen-storagealloy can be fully utilized and the absorption effect of thehydrogen-storage alloy can be improved.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (3), contacting the hydrogen-rich gas withthe hydrogen-storage alloy is carried out in one or morehydrogen-storage alloy storage containers; The number of thehydrogen-storage alloy(s) can be one or more, and a plurality ofhydrogen-storage alloys can be used in a mixture, or can be used inseries or in parallel or in combination of in series and in parallel;The pressure for contacting the hydrogen-rich gas with thehydrogen-storage alloy is 0.001-5 MPa (for example, 0.01-5 MPa, 0.03-4MPa, 0.05-5 MPa, 0.08-2 MPa, 0.05-3 MPa, 0.1-1 MPa), in case of aplurality of hydrogen-storage alloy storage containers and in thepresence of hydrogen-storage containers in series, in the hydrogen-richgas stream direction, the contact pressure for finally contacting withthe hydrogen-storage alloy (also known as the hydrogen absorptionpressure) is 0.05-5 MPa (for example 0.1-1 MPa); The temperature forcontacting the hydrogen-rich gas with the hydrogen-storage alloy (alsoknown as hydrogen absorption temperature) is −70 to 100° C. (forexample, −50 to 90° C., −30 to 80° C.); In case of contacting with thehydrogen-storage alloy, the temperature of the hydrogen-rich gas islower than the boiling temperature of the organic liquidhydrogen-storage material under normal pressure.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (3), the number of the hydrogen-storage alloystorage container(s) is one or more, wherein according to the order ofcontacting with hydrogen gas, the hydrogen-storage alloy in thehydrogen-storage alloy storage container finally contacting withhydrogen gas is a hydrogen-storage alloy having a high equilibriumpressure, wherein the hydrogen-storage alloy having a high equilibriumpressure is such one that there is at least one temperature pointbetween 150 and 450° C., and at this temperature point the equilibriumpressure for absorbing hydrogen gas is 35 MPa or higher; preferably thehydrogen-storage alloy in at least one hydrogen-storage alloy storagecontainer is a hydrogen-storage alloy having a high equilibriumpressure. High-purity and high-pressure hydrogen gas can be obtainedwith the hydrogen-storage alloy having a high equilibrium pressure, andthe obtained high-purity and high-pressure hydrogen gas can be directlyused for refueling the hydrogen fuel cell vehicle. According to theprocess for providing a high-purity hydrogen gas of the presentinvention, step (3a) is performed, wherein the organic substance in thehydrogen-containing alloy storage container is removed by a purgeprocess. For example the purge is performed with hydrogen gas, forexample the process is as follows: after the hydrogen-storage alloyreaches a predetermined adsorption capacity, the supply of ahydrogen-rich gas to the hydrogen-storage alloy is stopped, a hydrogengas is passed through the hydrogen-containing alloy, the organic gas inthe hydrogen-containing alloy and in the hydrogen-containing alloystorage container (also known as hydrogen-storage alloy storagecontainer) is taken out, and introduced into a storage tank for storageor absorbed by the hydrogen-storage alloy in other hydrogen-storagealloy storage containers; wherein preferably, the purity of the hydrogengas for purge is greater than 90 wt %, more preferably greater than 95wt %, for example greater than 99 wt %.

According to the process for providing a high-purity hydrogen gas of thepresent invention, in step (4): the temperature of hydrogen gas releasedby the hydrogen-storage alloy (namely, the temperature at which thehydrogen-storage alloy is heated, abbreviated as hydrogen releasetemperature) is 150 to 450° C., the pressure of the released hydrogengas is ≥35 MPa (for example, 35-100 MPa) in order to obtain ahigh-purity and high-pressure hydrogen, or the partial pressure of thereleased hydrogen gas is 0.1-5 MPa in order to obtain a high purityhydrogen gas, wherein the hydrogen release temperature is higher thanthe hydrogen absorption temperature.

According to the process for providing a high-purity hydrogen gas of thepresent invention, it further comprises the hydrogen-containing alloy isallowed to release hydrogen gas, and the released hydrogen contacts withdifferent hydrogen-storage alloy(s) to form hydrogen-containingalloy(s), and this process is repeated once or multiple times, whereinthe hydrogen-storage alloy used in at least the last repetition processis a hydrogen-storage alloy having a high equilibrium pressure

According to the process for providing a high-purity hydrogen gas of thepresent invention, the hydrogen-storage alloy is a combination of afirst hydrogen-storage alloy and a second hydrogen-storage alloy; Thefirst hydrogen-storage alloy is the magnesium-based A₂B typehydrogen-storage alloy according to the present invention for contactingwith the hydrogen-rich gas. The second hydrogen-storage alloy is used topressurize a first hydrogen-storage hydrogen gas, and the secondhydrogen-storage alloy is a hydrogen-storage alloy having a highequilibrium pressure, and the second hydrogen-storage alloy is one ormore of rare earth-based AB₅ type, zirconium-titanium-based AB: type,and titanium-based AB type hydrogen-storage alloys according to thepresent invention; The hydrogen-rich gas is firstly passed through thefirst hydrogen-storage alloy for impurity separation; then thehigh-purity hydrogen gas released from the first hydrogen-storage alloyis contacted with the second hydrogen-storage alloy, and then the secondhydrogen-storage alloy is allowed to release hydrogen gas under highpressure. The hydrogen release temperature of the first hydrogen-storagealloy is higher than the hydrogen absorption temperature of the secondhydrogen-storage alloy, and the temperature difference is preferably≥100° C. (for example, 350° C. ≥temperature difference ≥150° C.); Thefirst hydrogen-storage alloy and the second hydrogen-storage alloy arein different hydrogen-storage alloy storage tanks, and there is a heatexchange system between the first hydrogen-storage alloy storage tankand the second hydrogen-storage alloy storage tank; The hydrogenabsorption temperature for contacting the hydrogen-rich gas with thefirst hydrogen-storage alloy is 20-150° C. (for example, 50-100° C.),and the hydrogen gas partial pressure is 0.001-0.1 MPa (0.001-0.03 MPa);The temperature at which the first hydrogen-storage alloy releaseshydrogen gas (hydrogen release temperature) is 150 to 450° C. (forexample, 200-350° C.), and the hydrogen gas partial pressure forhydrogen release is 0.1-5 MPa (for example, 0.1-1 MPa); The hydrogenabsorption temperature at which the second hydrogen-storage alloyabsorbs hydrogen gas is-7( )to 100° C. (for example, −30 to 100° C.),and the hydrogen gas partial pressure for hydrogen absorption is 0.1-5MPa (for example, 0.1-1 MPa). The hydrogen release temperature of thesecond hydrogen-storage alloy is 150-450° C. (for example, 200-350° C.),and the hydrogen gas partial pressure for hydrogen release is ≥35 MPa(for example, 35-100 MPa).

According to the process for providing a high-purity hydrogen gas of thepresent invention, the organic liquid hydrogen-storage material is anorganic compound containing a ring in the molecule, which optionallycontains heteroatom(s), and the heteroatom(s) may be on the ring; Forexample, saturated or unsaturated hydrocarbons containing cycloalkanering(s), for example, saturated or unsaturated hydrocarbons containingno heterocyclic atom and containing cycloalkane ring(s), morespecifically, saturated or unsaturated hydrocarbons containing noheterocyclic atom and containing cycloalkane ring(s) and having thetotal ring number of aromatic rings and cycloalkanes of 2 or less, forexample, cyclohexane, methyl cyclohexane, decahydronaphthalene, andbi(cyclohexane); And saturated or unsaturated hydrocarbons containingheteroa.tom(s) and containing cycloalkane ring(s), for example,nitrogen-containing heterocyclic compounds, andnitrogen/boron-containing heterocyclic compounds, thenitrogen-containing heterocyclic compound comprises one or more ofdeeahydrocarbazole, dodecahydroethylcarbazole, indoline, 4-aminopiperidine; piperidine-4-carboxamide, perhydro-4,7-phenanthroline.2-methyl-1,2,3,4-tetrahydroquinoline, and2,6-dimethyldecahydro-1,5-naphthyridine; The nitrogen/boron-containingheterocyclic compound comprises one or more of 1,2-azaborinane, and3-methyl-1,2-azaborolidine.

According to the process for providing a high-purity hydrogen gas of thepresent invention, the process further comprises the released hydrogengas is introduced into a hydrogen gas storage tank to store hydrogengas; or the obtained high-purity and high-pressure hydrogen gas can bedirectly used to refuel a hydrogen fuel cell vehicle.

In an aspect of the present invention, the present invention provides ahigh-efficiently distributed process for producing high-purity andhigh-pressure hydrogen gas, the process comprising: in a dehydrogenationreactor, a liquid organic hydrogen-storage material is subjected todehydrogenation reaction in the presence of a dehydrogenation catalyst,to obtain a dehydrogenation reaction product including hydrogen gas; ina cooling separation apparatus, the dehydrogenation reaction product iscooled and separated to obtain a hydrogen-rich stream and an organicliquid; in a hydrogen-storage alloy storage container, a hydrogen-richstream or a purified hydrogen-rich stream is contacted with thehydrogen-storage alloy to obtain a hydrogen-containing alloy; purgingwith hydrogen gas removes an organic substance in the hydrogen-storagealloy storage container; wherein the purity of the hydrogen gas forpurge is preferably greater than 90 wt % (for example, greater than 95wt %, greater than 99 wt %); the hydrogen-containing alloy is heated torelease hydrogen gas to obtain a high-pressure hydrogen gas and supplythe obtained high-pressure hydrogen gas to a hydrogen-consumingapparatus or a high-pressure hydrogen gas storage tank for storage,forexample, the obtained high-pressure hydrogen gas can be directly used torefuel a hydrogen fuel cell vehicle.

In an aspect of the present invention, the present invention provides asystem for providing a high-purity and high-pressure hydrogen gas,comprising: an organic liquid hydrogen-storage material storage andsupply apparatus, used to store an organic liquid hydrogen-storagematerial and provide the organic liquid hydrogen-storage material to adehydrogenation reactor; a dehydrogenated liquid storage apparatus, usedto store the liquid product obtained after the dehydrogenation of theorganic liquid hydrogen-storage material; a dehydrogenation reactorapparatus, used for the dehydrogenation reaction of the organic liquidhydrogen-storage material under the action of the dehydrogenationcatalyst to obtain a dehydrogenation reaction product including hydrogengas; a cooling separation apparatus, used to separate thedehydrogenation reaction product to obtain a hydrogen-rich gas productand a liquid product; a hydrogen-storage & hydrogen-supply apparatus,which includes a hydrogen-storage alloy storage container and ahydrogen-storage alloy heating system; used to contact the hydrogen-richgas with the hydrogen-storage alloy to adsorb hydrogen gas at lowtemperature and low pressure, and heat to dehydrogenate after theadsorption is saturated; optionally, a purge apparatus, used to removeorganic substances) in the hydrogen-storage container; a hydrogen gassupply apparatus, supplying a high-pressure hydrogen to thehydrogen-consuming apparatus or the hydrogen gas storage tank;preferably, the system is configured to be integrated and built in acargo container, and used as a cargo container-type hydrogen productionsystem in a hydrogen refueling station, or directly built in a hydrogenrefueling station for use; preferably, the hydrogen-storage &hydrogen-supply apparatus comprises one or more hydrogen-storage alloystorage containers, a plurality of hydrogen-storage alloy storagecontainers can be connected in parallel or in series or in combinationof in series and in parallel; preferably, at least one of thehydrogen-storage alloy storage containers is a high-pressure-resistantcontainer and/or the hydrogen gas supply apparatus is ahigh-pressure-resistant apparatus, for example, its tolerance pressureis 35 MPa or more.

As shown in FIG. 3, the present invention provides a system forproviding a high-purity and high-pressure hydrogen gas, wherein: 1 is anorganic liquid storage tank, 2 is a material pump, 3 is a heatexchanger, 4 is a dehydrogenation reactor, 5 is a heat exchanger, 6 is ahydrogen-storage tank, 7 is a one-way valve, 8 is an energy transfersystem, 9 is a purge system, and 10 is a hydrogen-storage controlsystem; The organic liquid material storage system described in FIG. 3includes an organic liquid storage tank (1) and a material pump (2)connected to the organic liquid dehydrogenation reactor, the organicliquid storage tank is provided with an organic liquid material inletand an organic liquid material outlet; The organic liquiddehydrogenation reaction system includes an organic liquid heatexchanger (3) and a dehydrogenation reactor (4), and the organic liquidheat exchanger is connected to the outlet and the inlet of the organicliquid dehydrogenation reactor for cooling the reactor outlet gas andpreheating the material; The reactor outlet gas can be subjected to afurther heat-exchanging and cooling (5) to produce a hydrogen-richstream by the separation after cooling, and the hydrogen-rich stream canoptionally pass through one or more of the membrane separation apparatusand the pressure swing adsorption apparatus; The purification andpressurization system includes one or more sets of hydrogen-storagetanks (6), wherein each set of hydrogen-storage tanks is connected to aset of backflow prevention devices (7), and the hydrogen-storage tanksare connected in parallel to at least one hydrogen supply pipeline; atleast includes one energy delivery system (8), used to provide energy toeach hydrogen-storage tank to resolve hydrogen gas from the solidhydrogen-storage materials; at least includes a set of vacuum pumps (9)and a purge system, used to remove the impurity gases from thehydrogen-storage tank; the inlet and outlet of the hydrogen-storage tankare each connected to flow meters; and includes a control system (10),which overall controls the hydrogen absorption and release time of eachhydrogen-storage tank and the startup time of the energy deliverysystem, based on the hydrogen production volume of the dehydrogenationreaction. The inlet flow meter of the hydrogen-storage tank is used tocalculate the total hydrogen absorption amount of the hydrogen-storagealloy. When the hydrogen-storage capacity of the hydrogen-storage alloyin a single hydrogen-storage tank reaches 80% or more of the totalsaturated hydrogen absorption amount, the inlet valve of thehydrogen-rich stream of the hydrogen-storage tank is closed. The purgesystem is opened to remove impurities in the hydrogen-storage tank. Whenthe purity of hydrogen gas in the purge pipeline reaches 99% or more,the purge system is closed. The total amount of hydrogen absorbed by thehydrogen-storage tanks at the same time should be higher than 120% ofthe hydrogen generation rate, the hydrogen-storage alloy is connected toat least one hydrogen supply pipeline through a hydrogen dischargevalve, the hydrogen supply pipeline transports hydrogen gas to thehydrogen gas-storage apparatus, and the hydrogen discharge valves forhydrogen-storage alloys on hydrogen supply pipeline cannot beclosed/opened at the same time.

In an aspect of the present invention, the present invention provides amobile hydrogen supply system, comprising a transportation vehicle and asystem for providing a high-purity and high-pressure hydrogen gasaccording to the present invention arranged on the transportationvehicle.

In an aspect of the present invention, the present invention provides adistributed hydrogen supply apparatus, comprising a system for providinga high-purity and high-pressure hydrogen gas according to the presentinvention, and optionally comprising a high-pressure hydrogen gasstorage tank.

The process for preparing high-purity hydrogen gas provided by thepresent invention can efficiently provide high-purity hydrogen gas, andcan provide high-purity and high-pressure hydrogen gas in case of usinga hydrogen-storage alloy with high equilibrium pressure. In addition,the present invention may also have at least one of the followingbeneficial technical effects, and preferably has multiple beneficialtechnical effects:

(1) The process of the present invention can have higher dehydrogenationefficiency of organic liquid hydrogen-storage compounds.

(2) It can have a higher dehydrogenation conversion rate of organicliquid hydrogen-storage compounds.

(3) It can have higher dehydrogenation selectivity of organic liquidhydrogen-storage compounds.

(4) It has higher hydrogen absorption efficiency of hydrogen-storagemetal.

(5) Hydrogen-storage metal has good hydrogen absorption efficiency inthe presence of organic substance.

(6) Through the coupling of organic substance dehydrogenation, coolingseparation and hydrogen absorption with hydrogen-storage alloys, theeffect of increasing the conversion rate of organic substancedehydrogenation can be achieved.

(7) Dehydrogenation of organic materials and hydrogen absorption ofhydrogen-storage alloys can be more efficiently matched

The dehydrogenation catalyst for the dehydrogenation of organicsubstance to produce hydrogen gas provided by the present invention hasthe merits of higher dehydrogenation activity, hydrogen selectivityand/or hydrogen generation rate.

The dehydrogenation catalyst for hydrogen production from organicsubstance dehydrogenation provided by the present invention can replacepart of noble metals with non-noble metals, can reduce the amount ofnoble metals, and maintain high dehydrogenation activity, hydrogenselectivity and/or hydrogen generation rate.

The catalyst provided by the present invention can be used for thedehydrogenation of organic hydrogen-storage compounds to producehydrogen gas, especially for the dehydrogenation of organic substancescontaining rings, such as cycloalkane rings or heteroatom-containingrings, to produce hydrogen gas. It has higher conversion rate,selectivity and/or hydrogen generation rate.

According to the present invention, the percentage of the crystal phaseof the modified metal oxide can be measured by the ⁻following process:the X-ray diffraction and phase filtering, and an adapted form ofRietveld modeling, the content by weight percent of the crystal phase ofthe modified metal oxide was obtained by calculation with the fittingmethodology; reference is made to R. V. Siriwardane, J. A. Poston, G.Evans, Jr. Ind. Eng. Chem. Res. 33(1994),2810-2818 for phase filtering,and reference is made to RIQAS rietveld Analysis, Operators Manual,Material Data, Inc., Berkley, Calif. (1999) for the adapted form ofRietveld modelling.

According to the present invention, the chemical composition percentageof the modified metal oxide is the total content of the modified metaloxide in the support composition, and the chemical compositionpercentage of the modified metal oxide can be determined by. X-rayfluorescence method or chemical analysis process.

According to the present invention, the content by weight percent of themodified metal oxide on the surface of the support composition ismeasured by the XPS process, and the measured thickness of the surfacelayer is in the range from the outer surface to a level of 5 nm awayfrom the outer surface.

In addition, the present invention further provides the followingtechnical solutions:

1. A support composition for a catalyst of the dehydrogenation of anorganic substance to produce hydrogen gas, wherein the supportcomposition comprises alumina and a modified metal oxide, and themodified metal oxide is titanium oxide and/or zirconium oxide, whereinthe modified metal oxide has η<0.3, wherein η=the content by weightpercent of the crystal phase of the modified metal oxide in the supportcomposition/the content by weight percent of the chemical composition ofthe modified metal oxide in the support composition, titanium oxide iscalculated as TiO₂, zirconium oxide is calculated as ZrO₂.

2. The support composition according to solution 1, wherein η=0,preferably, the first metal oxide in a monolayer is dispersed on thealumina substrate.

3. The support composition according to solution 1, wherein in saidsupport composition, the mass fraction of alumina is 80-98.5%,preferably 83-97.5% or 85-95% or 90-95%; the mass fraction of themodified metal oxide is 1.5-20%, preferably 2.5-17% or 5-15%, or 5-10%.

4. The support composition according to solution 3, wherein the modifiedmetal oxide comprises titanium oxide, wherein preferably, in the supportcomposition, the mass fraction of titanium dioxide is preferably 2-20%for example 5-15% or 5-10% or 2.5-17%, the mass fraction of zirconiumdioxide is preferably 0-8% for example 0-6% or 0-3% or 1-6%.

5. The support composition according to solution 4, wherein relative tothe pure phase of TiO₂, in the XPS spectrum of the support composition,there is a shift for the Ti 2P_(3/2) orbital electron binding energy,the peak having the binding energy of 458.8 eV is shifted by 0.6-0.7 eVto a higher binding energy and reaches 459.4-459.5 eV, and/or a peak atthe Ti 2P_(1/2) orbital electron binding energy of 464.5 eV is shiftedby 0.8-0.9 eV to a higher binding energy and reaches 465.3-465.4 eV.

6. The support composition according to solution 1, wherein the oxidesubstrate has at least one phase structure of γ-alumina, η-alumina,ρ-alumina or χ-alumina.

7. The support composition according to solution 1, wherein the supportcomposition has a specific surface area of 100-350 m²/g.

8. The support composition according to solution 1, wherein said supportcomposition has a pore volume of 0.3-1.3 mL/g.

9. A process for preparing the support composition, comprising thefollowing steps:

(1) contacting an alumina substrate with gas flow of a modified metaloxide precusor carried by a gas, and when titanium tetrachloride reachesthe predetermined loading, the introduction of the gas flow of amodified metal oxide precusor carried by a gas is stopped, to obtain analumina substrate loaded with the modified metal oxide precusor, and themodified metal oxide precusor is titanium oxide precusor and/orzirconium oxide precusor;

(2) Hydrolyzing and calcining the alumina substrate loaded with themodified metal oxide precusor to obtain a support composition.

10. The process for preparing the support composition according tosolution 9, wherein said titanium oxide precusor is selected fromtitanium tetrachloride, ethyl titanate, isopropyl titanate, titaniumacetate, and a mixture thereof, preferably titanium tetrachloride; saidzirconium oxide precusor is selected from zirconium tetrachloride,zirconium ethoxide, zirconium methoxide, zirconium isopropoxide,tetrabutyl zirconate, and a mixture thereof, preferably zirconiumtetrachloride and/or zirconium methoxide.

11. The process for preparing the support composition according tosolution 9, wherein the alumina substrate is one or more of γ-alumina,η-alumina, ρ-alumina, and χ-alumina.

12. The process for preparing the support composition according tosolution 9, wherein said alumina substrate has a specific surface areaof 100-350 m²/g; wherein, pmferably, the specific surface area of theobtained support composition, compared with the specific surface area ofthe alumina substrate; is reduced by a proportion of ≤10%.

13. The process for preparing the support composition according tosolution 9, whereinSaid alumina substrate has a pore volume of 0.3-1.3ml/g.

14. The process for preparing the support composition according tosolution 9, Wherein the gas is an anhydrous inert gas, the content ofwater in the anhydrous inert gas is not more than 10 ppm. Preferably,the content of the modified metal oxide precusor in said gas flow of amodified metal oxide precusor carried by a gas is 0.1-3g /0.1-3 g/L,wherein the content of the modified metal oxide precusor is calculatedas metal oxide.

15. The process for preparing the support composition according tosolution 9, wherein in step (1), the temperature of said gas is roomtemperature to 350° C., for example room temperature to 300° C. or15-300° C.

16. The process for preparing the support composition according tosolution 9, wherein the pressure for contacting in step (1) is 0.05-5atm for example 1-3 atm.

17. The process for preparing the support composition according tosolution 9, wherein the ratio of the volumetric flow rate of the gas perminute to the volume of alumina substrate is 3-80 : 1 for example 5-30:1preferably 10-25:1; wherein the volume of the gas is calculated as thevolume under normal conditions, the volume of the alumina substrate iscalculated as the bulk volume.

18. The process for preparing the support composition according tosolution 9, wherein when the alumina substrate is contacted with the gasflow of a modified metal oxide precusor carried by a gas, the aluminasubstrate is in fluidized state or under stirring; wherein being influidized state may be, for example, in a bubbling bed, a turbulent bed,a fast bed or a conveying bed.

19. The process for preparing the support composition according tosolution 9, wherein in step (2), hydrolyzing the alumina substrateloaded with the modified metal oxide precusor is performed as follows:the alumina substrate loaded with the modified metal oxide precusor iscontacted with a gas containing water vapor. In an embodiment, the ratioof the gas containing water vapor to the alumina substrate contactedtherewith (the ratio of the volume of the gas containing water vapor andthe bulk volume of the alumina substrate under normal conditions) is3-80:1 for example 5-30:1, preferably 10-25:1, the proportion of thewater vapor in the gas containing water vapor relative to the total gasvolume is 0.1 vol %-100 vol %, preferably 3 vol %-100 vol %, morepreferably 10 vol %-70 vol %; other gas(es) except water vapour can beinert gas or air. The hydrolysis time is for example 1 hour to 50 hours,preferably 2 hours to 30 hours. Usually, the hydrolysis time is greaterthan or equal to the loading time (the loading time refers to the timefor contacting alumina substrate with the gas flow of a modified metaloxide precusor carried by a gas).

20. The process for preparing the support composition according tosolution 9, wherein for said calcining, the calcining temperature is350° C.-700° C., and the calcining time is 0.5-12 hours.

21. A catalyst for the dehydrogenation of an organic substance toproduce hydrogen gas, wherein said catalyst comprises a supportcontaining alumina and a modified metal oxide, and an active metalcomponent, the modified metal oxide is titanium oxide and/or zirconiumoxide; the active metal component is an oxide of active metal and/or asimple substance of active metal. Said active metal is for example oneor more of VIIIB group metal, VIIB group metal, VB group metal, VIBgroup metal, IB group metal, rare earth element, alkaline earth metal,IVA group metal;

Preferably, the active metal comprises Pt and/or Ni, optionally otherelement(s). Preferably, the other element is one or more of V, Cr, Mn,Fe, Co, Ni, Cu, A Ce, Mo, Sn, Ca, Pt, Pd, Ru, Re, Rh, Ir, Os, Zn, P, andIn. Preferably, the support is the support composition according to anyof solutions 1-8 or the support composition prepared by the processaccording to any of solutions 9-20.

22. A catalyst for dehydrogenation of organic substance to producehydrogen gas, comprising a support and a loaded active metal component,wherein said support is the support composition according to any ofsolutions 1-8 or the support composition prepared by the processaccording to any of solutions 9-20, the active metal comprises Pt andoptionally other metal, the other metal can be a noble metal or anon-noble metal, said other metal is one or more of elements Pd, Ru, Re,Rh, Ir, Os, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Cu, and Ca.

23. The catalyst according to solution 22, wherein in the catalyst, thecontent of active metal is 0.1-20 wt % for example 0.1-15 wt %, thecontent of the support is 85-99.9 wt %, the content of Pt is 0.1-10 wt%. In the composition of the catalyst of the present invention, for thecontent of the active metal, the nobel metal is calculated as simplesubstance, and the non-noble metal is calculated as oxide.

24. The catalyst according to solution 22, wherein the other metal isone or more of Pd, Ru, Re, Rh, Ir, and Os.

25. The catalyst according to solution 24, wherein in the catalyst, thecontent of said active metal is 0.1-10 wt %, preferably 0.5-8 wt %; thecontent of said support is 90-99.9 wt %, preferably 92-99.5 wt %,

26. The catalyst according to solution 25, wherein in the catalyst, thePt content is 0.1-2 wt % for example 0.3-1.5 wt % or 0.5-1 wt %, thecontent of said other metal content is 0-9.9 wt % for example 0.1-2 or0.2-1 wt % or 0.1-0.8 wt %, the content of said support is preferably90-99.9 wt % for example 96-99.6 wt % or 98-99,5 wt % or 98.5-99.3 wt %.

27. The catalyst according to solution 22, wherein the other metal isone or more of Sn,V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca.

28. The catalyst according to solution 27, wherein in the catalyst, thePt content is 0.1-10 wt %, the content of said other metal content is0-15 wt %.

29. The catalyst according to solution 28, wherein in the catalyst, thePt content is 0.1-2 wt % for example 0.5-1.5 wt %, the content of othermetal is 0-15 wt % for example 1-10 wt % or 2-8 wt % or 3-7 wt %; thecontent of said support is preferably 85-99.9 wt % for example 90-99 wt% or 90-98 wt % or 92-97 wt %.

30. A catalyst for dehydrogenation of organic substance to producehydrogen gas, comprising a support and a loaded active metal component,wherein said support is the support composition according to any ofsolutions 1-8 or the support composition prepared by the processaccording to any of solutions 9-20, the active metal comprises nickel,optionally other metal, said other metal is one or more of Zn, Sn, Cu,Fe, Ag, p, In, Re, Mo, Co, Ca, and

31. The catalyst according to solution 30, wherein in the catalyst, themass fraction of said active metal is 5%-30%, the mass fraction of thesupport is 70-95%; the mass fraction of the support is preferably75-90%, the mass fraction of the active metal is preferably 10%-25%.

32. The catalyst according to solution 30, wherein in the catalyst, thecontent of nickel as oxide is 5-25 wt %, preferably 6-20 wt % forexample 7-15 wt % or 7-12. wt % or 811 wt %, the content of the othermetal as oxide is 0-15 wt % preferably 0-10 wt % for example 0.5-8 wt %or 1-5 wt %.

33. The process for preparing the catalyst according to any of solutions21-32, comprising:

(1) dissolving an active metal component precursor in water andimpregnating a support to obtain a support impregnated with the activemetal component precursor;

(2) Drying and calcining the support impregnated with the active metalcomponent precursor; Preferably, said support is the support compositionaccording to any of solutions 1-8 or the support composition prepared bythe process according to any of solutions 9-20.

34. The process for preparing the catalyst according to solution 33,wherein the active metal comprises a non-noble metal, and step (2)comprises: the support impregnated with the active component precursoris placed in an environment below −40° C. for 1 hour to 24 hours; andthen it is vacuum-dried to remove the water adsorbed on the support, andthen calcined to obtain the catalyst composition.

35. The process for preparing the catalyst according to solution 33,wherein said active metal component precusor is: one or more of metalnitrate, metal chloride, metal acetate, metal carbonate, metal acetatecomplex, metal hydroxide, metal oxalate complex, high-valent metal acidsalt.

36. The process for preparing the catalyst according to solution 32,wherein for step 2 said calcining: the calcining temperature is 400-700°C.; the calcining time is preferably 0.5-12 hours.

37. A process for using the catalytic composition, comprising a step ofcontacting an organic hydrogen-storage compound with saiddehydrogenation catalyst according to any of solutions 21-32 or thedehydrogenation catalyst prepared by the process according to any ofsolutions 33-36 to perform the dehydrogenation reaction to producehydrogen gas.

38. The process according to solution 37, wherein the dehydrogenationreaction temperature is 150-450° C., weight hourly space velocity 0.5-50⁻¹, reaction pressure 0.3-5 MPa, the contacting is performed in thepresence or absence of hydrogen gas, hydrogen-to-oil ratio (the molarratio of hydrogen gas introduced into the dehydrogenation reactor toorganic hydrogen-storage compound) is 0-10.

39. The process according to solution 37, wherein the organichydrogen-storage compound is saturated or unsaturated hydrocarboncontaining cycloalkane ring(s), for example, the organichydrogen-storage compound is one or more of cyclohexane, methylcyclohexane, decahydronaphthalene, bi(cyclohexane), decahydrocarbazole,dodecahydroethylcarbazole, indoline, 4-aminopiperidine,piperidine-4-carboxamide, perhydro-4,7-phenanthroline;2-methyl-1,2,3,4-tetrahydroquinoline,2,6-dimethyldecahydro-1,5-naphthyridine, 1,2-BN-cyclohexane,3-methyl-1,2-BN-cyclopentane.

In addition, the present invention further provides the followingtechnical solutions:

1. A process for providing a high-purity hydrogen gas, the processcomprises: contacting and reacting an organic liquid hydrogen-storagematerial with a dehydrogenation catalyst to obtain a dehydrogenationreaction product containing hydrogen gas;

The dehydrogenation reaction product is cooled to obtain a liquidproduct and a hydrogen-rich gas product, and the liquid product iscollected;

The hydrogen-rich gas is contacted with a hydrogen-storage alloy toobtain a hydrogen-containing alloy, and an unadsorbed gas is collected;

Optionally, an organic substance in the hydrogen-containing alloystorage container is removed;

The hydrogen-containing alloy is heated to release hydrogen gas toobtain the high purity hydrogen gas.

2. The process according to solution 1, wherein the hydrogen-rich gas isthe hydrogen-rich gas product or a hydrogen gas-containing gas Obtainedby further separation of the hydrogen-rich gas product, and the processfor the further separation includes temperature swing separation,membrane separation, pressure swing adsorption separation or acombination thereof.

3. The process according to solution 1 or 2, wherein the mass fractionof hydrogen gas in the hydrogen-rich gas is ≥80%, for example, 80-99%,preferably ≥85%, more preferably ≥90%.

4. The process according to solution 1, wherein the temperature forcontacting said hydrogen-rich gas with the hydrogen-storage alloy is −70to 100° C., preferably −50 to 90° C. more preferably −30 to 80° C.

5. The process according to solution 1, wherein, wherein the temperaturefor cooling the dehydrogenation reaction product is lower than theboiling temperature of the organic substance; preferably lower than theboiling temperature of the organic substance with the lowest boilingpoint among those being liquid at normal temperature and pressure.

6. The process according to any of solutions 1-5, wherein in case ofcontacting with the hydrogen-storage alloy, the temperature of thehydrogen-rich gas is lower than the boiling temperature of the organicliquid hydrogen-storage material under normal pressure.

7. The process according to solution Wherein the number of thehydrogen-storage alloy(s) can be one or more, and a plurality ofhydrogen-storage alloys can be used in a mixture, or can be used inseries or in parallel or in combination of in series and in parallel;the preferred pressure for contacting the hydrogen-rich gas with thehydrogen-storage alloy is 0.001-5 MPa for example 0.01-5 MPa or 0.03-4MPa or 0.05-5 MPa or 0.08-2 MPa or 0.0-0.5-3 MPa or 0.1-1 MPa.

8. The process according to solution 1, wherein contacting saidhydrogen-rich gas with the hydrogen-storage alloy is performed in thehydrogen-storage alloy storage container(s), the number ofhydrogen-storage alloy storage container(s) is one or more; the pressurefor contacting the hydrogen-rich gas with the hydrogen-storage alloy is0.05-5 MPa preferably 0.1-1 MPa;

In case of a plurality of hydrogen-storage alloy storage containers andin the presence of hydrogen-storage containers in series, preferably, inthe hydrogen-rich gas stream direction, the contact pressure for finallycontacting with the hydrogen-storage alloy is 0.05-5 MPa, preferably0.1-1 MPa.

9. The process according to solution 1, wherein the number of thehydrogen-storage alloy storage container(s) is one or more, whereinaccording to the order of contacting with hydrogen gas, thehydrogen-storage alloy in the hydrogen-storage alloy storage containerfinally contacting with hydrogen gas is a hydrogen-storage alloy havinga high equilibrium pressure, wherein the hydrogen-storage alloy having ahigh equilibrium pressure is such one that there is at least onetemperature point between 150 and 450° C., and at this temperature pointthe equilibrium pressure for absorbing hydrogen gas is 35 MPa or higher;preferably the hydrogen-storage alloy in at least one hydrogen-storagealloy storage container is a hydrogen-storage alloy having a highequilibrium pressure.

10. The process according to solution 1, wherein the process furthercomprises the hydrogen-containing alloy is allowed to release hydrogengas, and the released hydrogen contacts with different hydrogen-storagealloy(s) to form hydrogen-containing alloy(s), and this process isrepeated once or multiple times, wherein the hydrogen-storage alloy usedin at least the last repetition process is a hydrogen-storage alloyhaving a high equilibrium pressure.

11. The process according to any of solutions 1-10, wherein thehydrogen-storage alloy is one or more of rare earth-based AB₅ type,zirconium-titanium-based AB₂ type, titanium-based AB type,magnesium-based A₂B type and vanadium-based solid solution type alloys.

12. The process according to solution 11, wherein the rare earth-basedAB₅ type hydrogen-storage alloy specifically has the molecular formulaof: MmNix1Cox2Mnx3Fex4Alx5Snx6, wherein, 4.5≤x1+x2+x3+x4+x5+x6≤0.05,3≤x1≤0.05.5, preferably 3≤x1≤4.9, 0≤x2≤1.5, preferably 0.1≤x2≤1, 0≤1,0≤x3≤0.8, preferably 0.1≤x3≤0.6, 0≤x4≤0.8, preferably 0.1≤x4≤0.6,0≤x5≤0.75, preferably 0≤x5≤0.5, 0≤x6≤0.2, preferably 0≤x6≤0.15; Mm is amixed rare earth metal containing La, Ce, Pr, Nd, and Y with anexpression formula of Mm=Lay1Cey2Ndy3Pry4Yy5, y1+y2+y3+y4+y5=1,0.4≤y1≤1, preferably 0.4≤y1≤0.8, 0≤y2≤0.45, preferably 0.1≤y2≤0.45,0≤y3≤0.2, 0≤y4≤0.05, 0≤y5≤0.05.

13. The process according to solution 11, wherein thezirconium-titanium-based AB₂ type hydrogen-storage alloy, whereinA=Mgx1Cax2Tix3Zrx4Yx5Lax6, x1+x2+x3+x4+x5+x6=0.9-1.1, 0≤x1 ≤1.1,preferably 0.90≤x1≤0.05, 0≤x2≤0.7, preferably 0≤x2≤0.25, 0≤x3≤0.05,preferably 0.8≤x3≤1, 0≤x4≤0.05, preferably 0.85≤x4≤1, 0≤x5≤0.2,preferably 0≤x5≤0.05, 0≤x6≤0.2, preferably 0≤x6≤0.05, and x3 /(x3x4)≥0.7or x3/(x3x4)≤0.3; B=Vy1Cry2Mny3Fey4Coy5Niy6Cuy7,y1+y2+y3+y4+y5+y6+y7=1.9-2.1, 0≤y1≤2.1, preferably 0≤y1≤1.8, 0≤y2 ≤2.1,preferably 0≤y2≤1.85, 0≤y3≤2.1, preferably 0≤y3≤2.05, 0≤y4≤1.6,preferably 0≤y4≤1.5, 0≤y5≤0.5, preferably 0≤y5≤0.3, 0≤y6≤0.5, preferably0≤y6≤0.3, 0≤y7≤0.5, preferably 0≤y7≤0.2, and 1.7≤y1+y2+y3+y4≤2.1.

14. The process according to solution 11, wherein the AB typehydrogen-storage alloy, wherein A=Tix1Zrx2Yx3Lax4, x1+x2+x3+x4=0.85-1.1,0 x1≤1.1, preferably 0.90≤x1≤1.05, 0≤x2 ≤1.1, preferably 0≤x2≤0.5,0≤x3≤0.2, preferably 0≤x3≤0.05, 0≤x4≤0.2, preferably 0≤x4≤0.05;B=Vy1Cry2Mny3Fey4Coy5Niy6Cuy7, y1+y2+y3+y4=0.95-1.05, 0≤y1≤0.5,preferably 0≤y1≤0.2, 0≤y2≤0.8, preferably 0≤0.2, 0≤y3≤0.8, preferably0.05≤y3≤0.3, 0≤y4 ≤0.05, preferably 0.7≤y4≤0.05, 0≤y5≤0.35, preferably0≤y5≤0.10, 0≤y6≤0.45, preferably 0≤y6≤0.20, 0≤y7≤0.3, preferably0≤y7≤0.2.

15. The process according to solution 11, wherein the vanadium-basedsolid solution type hydrogen-storage alloy, having a specific molecularformula of: Ax1Bx2, x1+x2=1, 0.85≤x1≤0.95, preferably 0.90≤x1≤0.95,0.05≤x2≤0.15, preferably 0.05≤x2≤0.10; whereinA=Tiy1Vy2Zry3Nby4Yy5Lay6Cay7, y1+y2+y3+y5+y6+y7=1, 0≤y1≤0.9, preferably0≤y1≤0.8, 0≤y2≤0.95, preferably 0≤y2≤0.95, 0≤y3≤0.90, preferably y3≤0.8,0≤y4≤≤0.55, preferably 0≤y4≤0.4, 0≤y5 ≤0.2, preferably 0.25≤y5≤0.05,0≤y6≤0.1, preferably 0≤y6≤0.05, 0≤y7≤0.1, preferably 0≤y7≤0.05,B=Mnz1Fez2Coz3Niz4, z1+z2+z3+z4=1, 0≤z1≤1, preferably 0≤z1≤0.95, 0≤z2≤0.95, preferably 0≤z2≤0.95, 0.7≤z1+z2≤1.0, 0≤z3≤0.3, preferably0≤z3≤0.2, 0≤z4≤0.45, preferably 0≤z4≤0.3.

16. The process according to solution 1 or 11, wherein thehydrogen-storage alloy is a combination of a first hydrogen-storagealloy and a second hydrogen-storage alloy; wherein, the firsthydrogen-storage alloy is a magnesium-based A₂B type hydrogen-storagealloy for contacting with the hydrogen-rich gas, the secondhydrogen-storage alloy is used to pressurize a first hydrogen-storagehydrogen gas, and the second hydrogen-storage alloy is ahydrogen-storage alloy having a high equilibrium pressure.

17. The process according to solution 16, wherein the secondhydrogen-storage alloy is one or more of rare earth-based AB₅ type,zirconium-titanium-based AB₂ type, titanium-based AB type alloys.

18. The process according to solution 1 or 16, wherein the hydrogen-richgas is firstly passed through the first, hydrogen-storage alloy forimpurity separation; then the high-purity hydrogen gas released from thefirst hydrogen-storage alloy is contacted with the secondhydrogen-storage alloy, and then the second hydrogen-storage alloy isallowed to release hydrogen gas under high pressure.

19. The process according to solution 16, wherein the hydrogen releasetemperature of the first hydrogen-storage alloy is higher than thehydrogen absorption temperature of the second hydrogen-storage alloy,and the temperature difference is preferahly ≥100° C., preferably 350°C. ≥temperature difference≥150° C.

20. The process according to solution 16, wherein the firsthydrogen-storage alloy and the second hydrogen-storage alloy are indifferent hydrogen-storage alloy storage tanks, and there is a heatexchange system between the first hydrogen-storage alloy storage tankand the second hydrogen-storage alloy storage tank.

21. The process according to solution 16 or 17, wherein said A₂B typefirst hydrogen-storage alloy, specifically having a molecular formulaof: A=Mgx1Cax2Tix3Lax4Yx5, x1+x2+x3=1.9-2.1, 1.5≤x1≤2.1, preferably1.70≤x1≤2.05, 0≤x2≤0.5, preferably 0≤x2≤0.2, 0≤x3≤0.8, preferably0≤x3≤0.50; B=Cry1Fey2Coy3Niy4Cuy5Moy6, y1+y2+y3+y4+y5+y6=0.9-1.1,0≤y1≤0.30, preferably 0≤y1≤0.2, 0≤y2≤0.20, preferably 0≤x2≤0.10, 0≤y3≤1.1, preferably 0≤y3≤1, 0≤y4 ≤1.1, preferably 0≤y4≤0.05, 0≤y5≤0.4,0≤y6≤0.15, preferably 0≤y6≤0.10;

Said AB₅ type second hydrogen-storage alloy, specifically has themolecular formula of: MmNix1 Cox2Mnx3Fex4Alx5Snx6, wherein,4.5≤x1+x2+x3+x4+x5+x6≤0.05.5, 3≤x1≤0.05.5, preferably 3≤x1≤4.9,0≤x2≤1.5, preferably 0.1≤x2≤1, 0≤x3≤0.8, preferably 1≤x3≤0.6, 0≤x4≤0.8,preferably 0.1≤x4≤0.6, 0≤x5≤0.75, preferably 0≤x5≤0.5, 0≤x6≤0.2,preferably 0≤x6≤0.15; Mm is a mixed rare earth metal containing La, Ce,Pr, Nd, and Y with an expression formula of Mm=Lay1Cey2Ndy3Pry4Yy5,y1+y2+y3+y4+y5=1, 0.4≤y1≤1, preferably 0.4≤y1≤0.8, 0≤y2≤0.45, preferably0.1≤y2≤0.45, 0≤y3≤0.2, 0≤y4≤0.05, 0≤y5≤0.05;

The zirconium-titanium-based AB₂ type alloy, the second hydrogen-storagealloy, wherein A=Mgx1Cax2Tix3Zrx4Yx5Lax6, x1+x2+x3+x4+x5+x6=0.9-1.1,0≤x1≤1.1, preferably 0.90≤x1≤0.05, 0≤x2 ≤0.7, preferably 0≤x2≤0.25, 0≤x3≤0.05, preferably 0.8≤x3≤1, 0≤x4≤0.05, preferably 0.85≤x4≤1, 0≤x5≤0.2,preferably 0≤x5≤0.05, 0≤x6≤0.2, preferably 0≤x6≤0.05, and x3/(x3+x4)≥0.7or x3/(x3+x4)≤0.3; B=Vy1Cry2Mny3Fey4Coy5Niy6Cuy7,y1+y2+y3+y4+y4+y5+y6+y7=1.9-2.1, 0≤y1≤2.1, preferably 0≤y1≤1.8, 0≤y2≤2.1, preferably 0≤y2≤1.85, 0≤y3 ≤2.1, preferably 0≤y3≤2.05, 0≤y4≤1.6,preferably 0≤y4≤1.5, 0≤y5 ≤0.5, preferably 0≤y5≤0.3, 0≤y6≤0.5,preferably 0≤y6≤0.3, 0≤y7 ≤0.5, preferably 0≤y7≤0.2, and1.7≤y1+y2++y3+y4≤2.1;

The titanium-based AB type alloy, the second hydrogen-storage alloy,wherein A=Tix1Zrx2Yx3Lax4, x1+x2+x3+x4=0.85-1.1, 0 x1≤1.1, preferably0.90≤x1≤0.05, 0≤x2 ≤1.1, preferably 0≤x2≤0.5, 0≤x3 ≤0.2, preferably0≤x3≤0.05, 0≤x4 ≤0.2, preferably 0≤x4≤0.05;B=Vy1Cry2Mny3Fey4Coy5Niy6Cuy7, y1+y2+y3+y4=0.95-1.05, 0≤y1 ≤0.5,preferably 0≤y l≤0.2, 0≤y2 ≤0.8, preferably 0≤y2≤0.2, 0≤y3 ≤0.8,preferably 0.05≤y3≤0.3, 0<y4≤1.05, preferably 0.7≤y4≤1.05, 0≤y5 ≤0.35,preferably 0≤y5≤0.10, 0≤y6≤0.45, preferably 0≤y6≤0.20, 0≤y7≤0.3,preferably 0≤y7≤0.2.

22. The process according to solution 16, wherein the temperature forcontacting the hydrogen-rich gas with the first hydrogen-storage alloyis 20-150° C., the hydrogen gas partial pressure is 0.001-0.1 MPa, thetemperature for the first hydrogen-storage alloy releasing hydrogen gas(hydrogen release temperature) is 150-450° C., the hydrogen gas partialpressure for the hydrogen release is 0.1-5 MPa.

23. The process according to solution 16 or 22, wherein the hydrogenabsorption temperature of the second hydrogen-storage alloy is-70 to100° C., the hydrogen gas partial pressure of the hydrogen absorption is0.1-5 MPa, the hydrogen release temperature of the secondhydrogen-storage alloy is 150-450° C., the hydrogen partial pressure ofthe hydrogen release≥35 MPa for example 35-100 MPa.

24. The process according to solution 16 or 22, wherein the hydrogenabsorption temperature for contacting the hydrogen-rich gas with thefirst hydrogen-storage alloy is preferably 50-100° C., the hydrogen gaspartial pressure is preferably 0.001-0.03 MPa; the hydrogen releasetemperature of the first hydrogen-storage alloy is preferably 200-350°C., the hydrogen gas partial pressure of the hydrogen release ispreferably 0.1-1 MPa; the hydrogen absorption temperature for the secondhydrogen-storage alloy absorbing hydrogen gas is preferably −30 to 100°C., the hydrogen gas partial pressure of the hydrogen absorption ispreferably 0.1-1 MPa, the hydrogen release temperature of the secondhydrogen-storage alloy is preferably 200-350° C., the hydrogen partialpressure of the hydrogen release is preferably ≥35 MPa.

25. The process according to solution 1, wherein the temperature for thehydrogen-storage alloy releasing hydrogen gas (the temperature forheating the hydrogen-storage alloy, abbreviated as hydrogen releasetemperature) is 150-450° C., the pressure of the released hydrogen gasis ≥35 MPa for example 35-100 MPa in order to obtain a high-purity andhigh-pressure hydrogen, or the hydrogen gas partial pressure for thehydrogen release is 0.1-5 MPa in order to obtain a high purity hydrogengas, wherein the hydrogen release temperature is higher than thehydrogen absorption temperature.

26. The process according to solution 1, wherein the organic substancein the hydrogen-containing alloy is removed by a purge process; thepurge is performed with hydrogen gas, for example the process is asfollows: after the hydrogen-storage alloy reaches a predeterminedadsorption capacity, the supply of a hydrogen-rich gas to thehydrogen-storage alloy is stopped, a hydrogen gas is passed through thehydrogen-containing alloy, the organic gas in the hydrogen-containingalloy and (also known as hydrogen-storage alloy storage container) istaken out, and introduced into a storage tank for storage or absorbed bythe hydrogen-storage alloy in other hydrogen-storage alloy storagecontainers; wherein preferably, the purity of the hydrogen gas for purgeis greater than 90 wt %, more preferably greater than 95 wt %, forexample greater than 99 wt %.

27. The process according to solution 1, wherein the reactiontemperature for contacting and reacting the organic liquidhydrogen-storage material with the dehydrogenation catalyst is 150-450°C., preferably 200-400° C., more preferably 300-350° C.

28. The process according to solution 1, wherein the weight hourly spacevelocity for contacting the organic liquid hydrogen-storage materialwith the dehydrogenation catalyst is 0.5-50 h⁻¹, preferably 1-45 h⁻¹more preferably 2-30 h⁻¹.

29. The process according to solution 1, wherein the pressure forcontacting and reacting the organic liquid hydrogen-storage materialwith the dehydrogenation catalyst is 0.03-5 MPa or 0.3-5 MPa, preferably0.1-3 MPa for example 0.5-2 MPa or 0.2-1.6 MPa.

30. The process according to solution 1, wherein the organic liquidhydrogen-storage material is mixed with hydrogen gas and then contactedwith the dehydrogenation catalyst, and the hydrogen-to-hydrocarbon ratio(the molar ratio of hydrogen gas to the organic liquid hydrogen-storagematerial) is 0-10.

31. The process according to solution 1, wherein the organic liquiddehydrogenation reaction in the presence or absence of hydrogen gas, theorganic liquid dehydrogenation reaction temperature is 150-450° C., theweight hourly space velocity 0.5-50 h⁻¹, the reaction pressure 0.3-5MPa, the hydrogen-to-hydrocarbon ratio is 0-10 molar ratio, thepreferred reaction temperature is 200-400° C., the weight hourly spacevelocity 1-30 h⁻¹, the hydrogen-to-hydrocarbon ratio is 0-8 molar ratio.

32. The process according to solution 1, wherein the dehydrogenationcatalyst is a metal-loaded type catalyst, the metal-loaded type catalystcomprise a support and a loaded active metal component; said support,said active metal preferably comprises one or more of Group VIII metals;more preferably, the active metal component contains a first activemetal and an optional second active metal, said first active metal isone or more of Pt, Pd, Ru, Rh, and Ir, said second active metal is oneor more of Ni, Re, Sn, Mo, Cu, Fe, Ca, Co, and W, said second activemetal is preferably one or more of Ni, Re, and Sn; more preferably, thefirst active metal comprises Pt;

or,

The dehydrogenation catalyst includes a support and a loaded activemetal component. The support is selected from one or more of alumina,silica, titanium dioxide, zirconium oxide, activated carbon, and siliconaluminum materials, and the active metal is selected from at least twometals of Ni, Zn, Sn, Cu, Fe, Ag, p, In, Re, Mo, Co, Ca, and W, and morepreferably two or more of Ni, Zn, Sn, and Cu, or the active metalincludes Ni and one or more selected, from Zn, Sn, Cu, Fe, Ag, p, In,Re, Mo, Co, Ca, and W.

33. The process according to solution 32, wherein the mass fraction ofthe support in the dehydrogenation catalyst is 70-99.9%, and the massfraction of the metal component is 0.1-30%.

34. The process according to solution 1, wherein the dehydrogenationcatalyst includes a support and an active metal component, and thesupport is a support composition, and the support composition includesalumina and a modified metal oxide, the modified metal oxide is titaniumoxide and/or zirconium oxide, wherein the modified metal oxide hasη<0.3, where η=the content by weight percent of the crystal phase of themodified metal oxide in the support composition/the content by ⁻weightpercent of the chemical composition of the modified metal oxide in thesupport composition, titanium oxide is calculated as TiO₂, and zirconiumoxide is calculated as ZrO₂.

35. The process according to solution 34, wherein the supportcomposition has η=0, preferably, the first metal oxide in a monolayer isdispersed on the alumina substrate.

36. The process according to solution 34, wherein in said supportcomposition, the mass fraction of alumina is 80-98.5%, pmferably83-97.5% or 85-95% or 90-95%; the mass fraction of the modified metaloxide is 1.5-20%, preferably 2.5-17% or 5-15%, or 5-10%.

37. The process according to solution 34, wherein the modified metaloxide comprises titanium oxide, wherein preferably, in the supportcomposition, the mass fraction of titanium dioxide preferably 2-20% forexample 5-15% or 5-10% or 2.5-17%, the mass fraction of zirconiumdioxide preferably 0-8% for example 0-6% or 0-3% or 1-6%.

38. The process according to solution 34, wherein relative to the purephase of TiO₂, in the XPS spectrum of the support composition, there isa shill for the Ti 2P_(3/2) orbital electron binding energy, the peakhaving the binding energy of 458.8 eV is shifted by 0.6-0.7 eV to ahigher binding energy and reaches 459.4-459.5 eV and/or a peak at the Ti21)1/2 orbital electron binding energy of 464.5 eV is shifted by 0.8-0.9eV to a higher binding energy and reaches 465.3-465.4 eV

39. The process according to solution 34, wherein the oxide substratehas at least one phase structure of ₇-alumina, malumina, ρ-alumina orχ-alumina.

40. The process according to solution 34, wherein the supportcomposition has a specific surface area of 100-350 m²1g,

41. The process according to solution 34, wherein said supportcomposition has a pore volume of 0,3-1,3 ml/g.

42. The process according to solution 1 or 34, wherein saiddehydrogenation catalyst comprises a support containing alumina and amodified metal oxide, and an active metal component, the modified metaloxide is titanium oxide and/or zirconium oxide; the active metalcomponent is an oxide of active metal and/or a simple substance ofactive metal. Said active metal is for example one or more of VIIIMgroup metal, VIIB group metal, VB group metal. VIB group metal, IB groupmetal, rare earth element, alkaline earth metal, IVA. group metal;

Preferably, the active metal comprises Pt and/or Ni, optionally otherelement; preferably, the other element is one or more of V, Cr, Mn, Fe,Co, ⁻Ni, Cu, Ag, Ce, W, Mo, Sn, Ca, Pt, Pd, Ru, Re, Rh, Ir, Os, Zn, P,and In.

43. The process according to solution 42, wherein the active metalcomprises Pt, optionally other metal, the other metal can be a noblemetal or a non-noble metal, said other metal is one or more of Pd, Ru,Re, Rh, Ir, Os, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, andCa.

44. The process according to solution 42, wherein in saiddehydrogenation catalyst, the content of active metal is 0.1-20 wt % forexample 0.1-15 wt %, the content of the support is 75-99.9 wt %, thecontent of Pt is 0.1-10 wt %; in the composition of the dehydrogenationcatalyst of the present invention, for the content of the active metal,the nobel metal is calculated as simple substance, and the non-noblemetal is calculated as oxide.

45. The process according to solution 43, wherein the other metal is oneor more of Pd, Ru, Re, Rh, Ir, and Os.

46. The process according to solution 43, wherein in saiddehydrogenation catalyst, the content of said active metal is 0.1-10 wt%, preferably 0.5-8 wt %; the content of said support is 90-99.9 wt %,is preferably 92-99.5 wt %.

47. The process according to solution 43, wherein in the catalyst, thePt content is 0.1-2 wt % for example 0.3-1.5 wt % or 0.5-1 wt %, thecontent of said other metal content is 0-9.9 wt % for example 0.1-2 or0.2-1 wt % or 0.1-0.8 wt %, the content of said support is preferably90-99.9 wt % for example 96-99.6 wt % or 98-99.5 wt % or 98.5-99.3 wt %.

48. The process according to solution 43, wherein the other metalelement is one or more of Sn, V. Mo,Cr, Mn, Fe, Co, LTi, Cu, g, C7e, W,Cu, and Ca.

49. The process according to solution 43, wherein in the catalyst, thePt content is 0.1-10 wt %, the content of said other metal content is0-15 wt %.

50. The process according to solution 43, wherein in the catalyst, thePt content is 0.1-2 wt % for example 0.5-1.5 wt %, the content of othermetal is 0-15 wt % for example 1-10 wt % or 2-8 wt % or 3-7 wt %; thecontent of said support is preferably 85-99.9 wt % for example 90-99 wt% or 90-98 wt % or 97-97 wt %.

51. The process according to solution 34, wherein the active metalcomprises nickel, and optionally other metal, said other metal is one ormore of Zn, Sn, Cu, Fe, Ag, p. In, Re, Mo. Co, Ca, and W.

52. The process according to solution 51, wherein in the catalyst, themass fraction of said active metal is 5%-30%, the mass fraction of thesupport is 70-95%; the mass fraction of the support is preferably75-90%, the mass fraction of the active metal is preferably 10%-25%.

53. The process according to solution 51, wherein in the catalyst, thecontent of nickel as oxide is 5-25 wt %, preferably 6-20 wt % forexample 7-15 wt % or 7-12 wt % or 8-11 wt %, the content of the othermetal as oxide is 0-15 wt % preferably 0-10 wt % for example 0.5-8 wt %or 1-5 wt %.

54. The process according to solution 1, wherein the organic liquidhydrogen-storage material is a saturated and/or unsaturated hydrocarboncontaining cycloalkane ring(s) and optionally containing heteroatom(s),and the heteroatom-containing organic hydrogen-storage compound is anorganic substance obtained by the substitution of a hydrocarboncontaining cycloa.lkane ring(s) by heteroatom(s), in which theheteroatom substitution occurs on the cycloalkane ring. Among them, theorganic liquid hydrogen-storage materials are preferably saturated orunsaturated hydrocarbons containing no heterocyclic atom and containingcycloalkane ring(s). More preferably saturated or unsaturatedhydrocarbon containing no heterocyclic atom and having the total ringnumber of aromatic rings and cycloalkanes of 2 or less;

More further preferably, the organic hydrogen-storage material issaturated or unsaturated hydrocarbon containing no heterocyclic atom andhaving the total ring number of aromatic rings and cycloalkanes of 2 orless; Saturated and unsaturated hydrocarbons containing no heteroatomand containing cycloalkane ring(s) comprise one or more of cyclohexane,methylcyclohexane, decahydronaphthalene, and bi(cyclohexane);Heteroatom-containing saturated or unsaturated hydrocarbons containingcycloalkane rings) comprise: nitrogen-containing heterocyclic compoundand nitrogen/boron-containing heterocyclic compound, for examplenitrogen-containing heterocyclic compound comprises one or more ofdecahy drocarbazole, dodecahydroethylcarbazole, indoline,4-aminopiperidine, pi peridine-4-carboxamide,perhydro-4,7-phenanthroline, 2-methyl-1,2,3,4-tetrahydroquinoline,2,6-dimethyldecahydro-1,5-naphthyridine, unsaturated hydrocarbonscontaining nitrogen/boron heteroatom comprise: one or more of1,2-BN-cyclohexane; and 3-methyl-1,2-BN-cyclopentane.

55. The process according to solution 1, characterized by furthercomprising introducing the released hydrogen gas into a hydrogen gasstorage tank to store the hydrogen gas; or the obtained high-purityhigh-pressure hydrogen gas can be directly used to refuel a hydrogenfuel cell vehicle.

56. A high-efficiently distributed process for producing high-purity andhigh-pressure hydrogen gas, the process comprising:

In a dehydrogenation reactor, a liquid organic hydrogen-storage materialis subjected to dehydrogenation reaction in the presence of adehydrogenation catalyst to obtain a dehydrogenation reaction productincluding hydrogen gas;

In a cooling separation apparatus, the dehydrogenation reaction productis cooled and separated to obtain a hydrogen-rich stream and an organicliquid;

In a hydrogen-storage alloy storage container, a hydrogen-rich stream ora purified hydrogen-rich stream is contacted with the hydrogen-storagealloy to obtain a hydrogen-containing alloy;

Purging with hydrogen gas removes an organic substance in thehydrogen-storage alloy storage container; wherein the purity of thehydrogen gas for purge is preferably greater than 90 wt %, morepreferably greater than 95 wt %;

The hydrogen-containing alloy is heated to release hydrogen gas toobtain a high-pressure hydrogen gas and supply the obtainedhigh-pressure hydrogen gas to a hydrogen-consuming apparatus or ahigh-pressure hydrogen gas storage tank for storage.

57. A system for providing a high-purity and high-pressure hydrogen gas,comprising:

An organic liquid hydrogen-storage material storage and supplyapparatus, used to store an organic liquid hydrogen-storage material andprovide the organic liquid hydrogen-storage material to adehydrogenation reactor;

A dehydrogenated liquid storage apparatus, used to store the liquidproduct obtained after the dehydrogenation of the organic liquidhydrogen-storage material;

A dehydrogenation reactor apparatus, used for the dehydrogenationreaction of the organic liquid hydrogen-storage material under theaction of the dehydrogenation catalyst to obtain a dehydrogenationreaction product including hydrogen gas;

A cooling separation apparatus, used to separate the dehydrogenationreaction product to obtain a hydrogen-rich gas product and a liquidproduct;

A hydrogen-storage & hydrogen-supply apparatus, which includes ahydrogen-storage alloy storage container and a hydrogen-storage alloyheating system, used to contact the hydrogen-rich gas with thehydrogen-storage alloy to adsorb hydrogen gas at low temperature and lowpressure, and heat to dehydrogenate after the adsorption is saturated;

Optionally, a purge apparatus, used to remove organic substance(s) inthe hydrogen-storage container;

A hydrogen gas supply apparatus, supplying a high-pressure hydrogen tothe hydrogen-consuming apparatus or the hydrogen gas storage tank.

58. The system according to solution 57, wherein the system isconfigured to be integrated and built in a cargo container, and used asa cargo container-type hydrogen production system in a hydrogenrefueling station, or directly built in a hydrogen refueling station foruse.

59. The system according to solution 57, wherein the hydrogen-storage &hydrogen-supply apparatus comprises one or more hydrogen-storage alloystorage containers, a plurality of hydrogen-storage alloy storagecontainers can be connected in parallel or in series or in combinationof in series and in parallel.

60. The system according to any of solutions 57-59, wherein at least oneof the hydrogen-storage alloy storage containers is ahigh-pressure-resistant container and/or the hydrogen gas supplyapparatus is a high-pressure-resistant apparatus. Preferably, itstolerance pressure is 35 MPa or more.

61. A mobile hydrogen supply system comprising a transportation vehicleand the system for providing high-purity hydrogen gas according to anyof solutions 57-60 arranged on the transportati on vehicle.

61. A distributed hydrogen supply apparatus, comprising the system forproviding high-purity hydrogen gas according to any of solutions 57-60and optionally comprising a high-pressure hydrogen gas storage tank.

EXAMPLES

The following examples will further illustrate the present invention,but they should not be used to limit the present invention.

Materials and Testing Methods

SB powder: Deutschland Sasol company, solid content 75 wt %.

P25 (titanium dioxide): Deutschland Degussa company, solid content 98 wt%.

Metal acid salts and metal salts were purchased from Sinopharm ChemicalReagent Beijing Co., Ltd.

Organic liquid hydrogen-storage materials were purchased from J&KScientific Co., Ltd.

In each of examples and comparative examples, the compositions of theloaded-type organic liquid dehydrogenation catalysts were determined byX-ray fluorescence method, and the dehydrogenation products of theorganic liquid hydrogen-storage materials were obtained bychromatographic analysis. The purity of hydrogen gas was analyzed by gaschromatography. The organic liquid dehydrogenation experiments of theexamples and the comparative examples of the present invention werecarried out in a fixed bed reactor.

For separation, a cooling medium was used to conduct the cooling andseparation, the hydrogen-storage container was connected after theseparation system, the energy delivery medium was hot water or hot watervapor, and the water vapor was generated by the water vapor generator.

In the following examples, in the preparation of the support for thedehydrogenation catalyst of the organic liquid hydrogen-storagematerial, the content by percent of the crystal phase of the modifiedmetal oxide was measured by the following process:

Philips XRG3100 generator equipped with a long fine focus copper X-raysource powered at 40 kV and 30 mA, Philips3020 digital goniometer,Philips3710MPD control computer and Kevex PSI Peltier cooled silicondetector were used for all X-ray diffraction measurements. Kevex4601 ionpump controller, Kevex4608Peltier power supply, Kevex4621 detector bias,Kevex4561A pulse processor and Kevex4911-A single-channel analyzer wasused to operate Kevex detector. Philips APD4.1C version software wasused to obtain diffraction patterns. All rietveld calculations wereperformed using Material Data, Inc. Riqas 3.1C version software(Qutokumpu HSC Chemistry for Windows; User Guide, Qutokumpo Resarch Oy,Pori, Finland (1999)).

In the following examples, XPS experiments were performed on ThermoFisher company's ESCALab250 type X-ray photoelectron spectroscopy. Theexcitation source was a monochromatic Al K α X-ray with an energy of1486.6 eV and a power of 150 W The transmission energy used for narrowscanning was 30 eV The base vacuum during analysis was about 6.5*10-10mbar. The binding energy was corrected by the Cls peak (284.8 eV) ofcontaminated carbon. The content by weight percent of the modified metaloxide on the surface of the support composition was determined bymeasuring 10 sample particles and taking the average value.

In the following examples, the specific surface area and the pore volumewere determined by the static cryosorption capacity method (according toGB/T5816-1995) using an automatic adsorption apparatus of ASAP 2400type, from Micromeritics instruments USA, and the specific method was asfollows: the object to be detected was vacuumized and degassed for 4hours at 250° C. and 1.33 Pa, and contacted with nitrogen serving asadsorbate at −196° C. until the static adsorption reached the adsorptionbalance; the amount of nitrogen adsorbed by the adsorbent was calculatedby the difference between the nitrogen gas intake amount and the amountof nitrogen remaining in the gas phase after adsorption, and then thespecific surface area and the pore volume were calculated by the BETequation.

Preparation of the Support for the Dehydrogenation Catalyst of theOrganic Liquid Hydrogen-Storage Material

Support Example 1

The SB powder was calcined at 500° C. for 4 hours to obtain γ-Al₂O₃. Thespecific surface area of γ-Al₂O₃ was 176 m²/g and the pore volume was0.48 mL/g.

The above γ-Al₂O₃ (500 g) was placed in a fluidized reactor (the innerdiameter: 10cm, the height: 40 cm), titanium tetrachloride was placed ina constant temperature bath at 20° C., nitrogen gas (25° C.) wasintroduced through titanium tetrachloride at a flow rate of 10 L/min andthen into the fluidized reactor from the bottom of the fluidizedreactor, the introduction of nitrogen gas through the titaniumtetrachloride bath was terminated after the fluidization was performedfor 1 hour; nitrogen gas (25° C.) was introduced through deionized water(placed in a constant temperature bath at 50° C.) at a flow rate of 10L/min and then into the fluidized reactor from the bottom of thefluidized reactor, the fluidization was performed for 4 hour forhydrolysis to obtain a hydrolyzed support. The hydrolyzed support wascalcined in an air atmosphere at 550° C. for 4 hours to obtain the finalsupport, which was named support 1. The support composition and supportproperties were shown in Table 1; and its X-ray diffraction (XRD)spectrum was shown as “1” in FIG. 1.

Support Examples 2-8

Supports 2-8 were prepared in the same way as support 1 in SupportExample 1, except for the time for which titanium tetrachloride wascarried by nitrogen gas into the fluidized bed, and the hydrolysis timefor which nitrogen gas was introduced into deionized water. The supportpreparation conditions, support composition and support properties wereshown in Table 1.

Support Examples 9-11

Supports 9-11 were prepared in the same way as support 1 in SupportExample 1, except that nitrogen gas was firstly passed through titaniumtetrachloride, and then through zirconium tetrachloride steam generator(its temperature was 300° C.). The support preparation conditions,support composition and support properties were shown in Table 1.

Support Comparative Example 1

SB powder was calcined at 500° C. for 4 hours directly to obtainγ-Al₂O₃, and the support was named support C1. The support compositionand support properties were shown in Table 1.

Support Comparative Example 2

The support was prepared by referring to the process of Support Example1, except that the γ-Al₂O₃ obtained by calcining SB powder at 500° C.for 4 hours was physically mixed with TiO₂, and the support was namedsupport C2. The support composition and support properties were shown inTable 1; and its X-ray diffraction (XRD) spectrum was shown as “2” inFIG. 1.

Support Comparative Example 3

The support was prepared by referring to the process of SupportComparative Example 2, and the support was named support C3. The supportcomposition and support properties were shown in Table 1.

Support Comparative Example 4

The support was prepared by referring to the process of Support Example6, except that the support γ-Al₂O₃ Obtained by calcining SB powder at500° C. for 4 hours was physically mixed with anaqueous titaniumtetrachloride solution, and the support was named support C4. Thesupport composition and support properties were shown in Table 1.

Support Comparative Example 5

The support was named support C5. The support composition and supportproperties were shown in Table 1; and its X-ray diffraction (XRD)spectrum was shown as “5” in FIG. 1.

Support Comparative Example 6

The support was prepared by referring to the formulation of SupportExample 9, except that the γ-Al₂O₃ obtained by calcining SB powder at500° C. for 4 hours was physically mixed with TiO₂ and ZrO₂. The supportwas named support C6. The support composition and support propertieswere shown in Table 1.

Support Comparative Example 7

The support was prepared by referring to Support Comparative Example 6,and the support was named support C7. The support composition andsupport properties were shown in Table 1.

The properties of the supports prepared in Support Examples 1-11 andSupport Comparative Examples 1-7 were shown in Table 1.

Preparation and Evaluation of the Dehydrogenation Catalyst of theOrganic Liquid Hydrogen-Storage Material

Example 1

0.34 g of chloroplatinic acid and water were prepared into 20 mL ofimpregnation liquor. The impregnation liquor was slowly added to 19.84 gof support 1 with stirring while adding to ensure that the impregnationliquor was uniformly loaded on the composite oxide support. Theimpregnation temperature was 25° C., the impregnated solid was dried for3 hours under purge at 120° C., and then calcined in air. The calciningtemperature was 600° C., the air-to-catalyst ratio (air/solid volumeratio) during calcining was 600:1, and the calcining time was 4 hours,and a catalyst was finally obtained. The composition of the catalyst waslisted in Table 2.

The dehydrogenation reaction of methylcyclohexane was performed in afixed bed reactor to evaluate the above-prepared catalyst. Thedehydrogenation reaction was carried out in a fixed bed microreactor.The evaluation conditions were: reaction temperature 350° C., reactionpressure (reactor inlet pressure) IMPa, make-up hydrogen flow rate 150mL/minH2, methylcyclohexane feedstock 2 mL/min; and catalyst loading 20g. The evaluation results of the catalyst were listed in Table 2,wherein the conversion rate=reacted methylcyclohexaneltotalmethylcyclohexane feedstock; the selectivity=toluene-producedmethylcyclohexanelreacted methylcyclohexane.

Example 5

In a manner similar to Example 1, chloroplatinic acid, nickel nitrateand water were prepared into 20 mL of impregnation liquor. Theimpregnation liquor was slowly added to 19.7 g of support 1 withstirring while adding to ensure that the impregnation liquor wasuniformly loaded on the composite oxide support. The impregnationtemperature was 25° C., the impregnated solid was dried for 3 hoursunder purge at 120° C., and then calcined in air. The calciningtemperature was 600° C., the air-to-catalyst ratio (air/solid volumeratio) during alcining was 600:1, and the calcining time was 4 hours,and a catalyst was finally obtained.

The composition of the catalyst was listed in Table 2.

The dehydrogenation reaction of tnethylcyclohexane was performed in afixed bed reactor to evaluate the above-prepared catalyst. Thedehydrogenation reaction was carried out in a fixed bed microreactor.The evaluation conditions were: reaction temperature 350° C., reactionpressure (reactor inlet pressure) 1MPa, make-up hydrogen flow rate 150mL/minH2, methylcyclohexane feedstock 2.5 mL/min, and catalyst loading20 g. The evaluation results of the catalyst were listed in Table 2,wherein the conversion rate=reacted methylcyclohexane/totalmethylcyclohexane feedstock; the selectivity=toluene-producedmethylcyclohexanelreacted methylcyclohexane.

Example 10

Nickel nitrate, tin chloride and water were prepared into 20 mL ofimpregnation liquor. The impregnation liquor was slowly added to 17.8 gof support 1 with stirring while adding to ensure that the impregnationliquor was uniformly loaded on the composite oxide support. Theimpregnation temperature was 25° C., the impregnated solid was dried for3 hours under nitrogen purge at 120° C., and then calcined in air. Thecalcining temperature was 600° C., the air-to-catalyst ratio (air/solidvolume ratio) during calcining was 600:1, and the calcining time was 4hours, and a catalyst was finally obtained. The composition of thecatalyst was listed in Table 2.

The dehydrogenation reaction of methylcyclohexane was performed in afixed bed reactor to evaluate the above-prepared catalyst. Thedehydrogenation reaction was carried out in a fixed bed microreactor.The evaluation conditions were: reaction temperature 400° C., reactionpressure (reactor inlet pressure) 1 MPa, make-up hydrogen flow rate 150mL/minH2, methylcyclohexane feedstock 1.0 mL/min, and catalyst loading20 g. The evaluation results of the catalyst were listed in Table 2,wherein the conversion rate=reacted methylcyclohexanaltotalmethylcyclohexane feedstock; the selectivity=toluene-producedmethylcyclohexanelreacted methylcyclohexane.

Examples 2, 4, 7-9 and 12-39 and Comparative Examples 1-17

According to Example 1, 5 or 10, the catalysts were prepared byimpregnation process. The catalyst formula were shown in Table 2. Thesupport was calculated on dry basis (calcined at 800° C. for 1 hour),platinum (Pt) was calculated on dry basis of simple substance, palladium(Pd) was calculated on dry basis of simple substance, iridium (Ir) wascalculated on dry basis of simple substance, rhenium (Re) was calculatedon dry basis of simple substance, nickel (Ni) was calculated as NiO, tin(Sn) was calculated as SnO2, zinc (Zn) was calculated as ZnO, copper(Cu) was calculated as CuO, iron (Fe) was calculated as Fe2O3, silver(Ag) was calculated as AgO, phosphorus (P) was calculated as P2O5, andmanganese (Mn) was calculated as MnO2.

According to the evaluation method of Example 1, 5 or 10, the preparedcatalysts were evaluated, and the evaluation conditions were as follows:reaction pressure (reactor inlet pressure) 1 MPa, and catalyst loadingamount 20 grams; reaction temperature, make-up hydrogen flow rate, andmethylcyclohexane feedstock were listed in Table 2.

Examples 3, 6 and 11

The catalysts of Examples 3, 6 and 11 were prepared according to theprocesss of Examples 2, 5 and 10 respectively, except that theimpregnated solid was frozen at −45° C. for 10 hours, and then driedat-5° C., under 0.latm (absolute pressure) vacuum condition, and thenthe calcining was performed.

According to the evaluation method of Example 1, the prepared catalystswere evaluated, and the evaluation conditions were as follows: reactionpressure (reactor inlet pressure) 1 MPa, and catalyst loading amount 20grams; reaction temperature, make-up hydrogen flow rate, andmethylcyclohexane feedstock were listed in Table

The dehydrogenation catalyst provided by the present invention couldhave higher conversion activity than the dehydrogenation catalystprepared by the existing process. Under the same reaction conditions, ithad a higher hydrogen generation rate. Using freezing and vacuum dryingprocesss, the activity and selectivity of the catalyst were increased,and the hydrogen generation rate was increased.

Preparation and Evaluation of the Hydrogen-Storage Alloy

Hydrogen-Storage Alloy Examples 1-13 and C1-C4

A total of about 1000 g of metals according to the alloy compositionwere weighed, placed in a water-cooled crucible of a vacuum inductionmelting furnace, and molten under vacuum to obtain an alloy, thepreparation conditions including: the melting was performed under abackground vacuum of 1*10⁻⁴ Pa, and the melting temperature and timewere shown in Table 3. The annealing was performed by lowering thetemperature to the annealing temperature at a rate of 10° C./min under abackground vacuum of 1*10⁻⁴ Pa, and the annealing temperature and timewere shown in Table 3. The nature cooling to room temperature wasperformed under a background vacuum of 1*10⁻⁴ Pa. The obtained alloy wascrushed and sieved to obtain 70-200 mesh metal powder. The powder wasput into a hydrogen-storage tank, and the hydrogen-storage tank washeated to 300° C. under a vacuum of 0.1 Pa for 4 hours to activate thealloy powder to obtain hydrogen-storage alloys 1-13 and C1-C4.

1 kg of hydrogen-storage alloy was placed in a hydrogen-storage tank,and a hydrogen gas containing organic substances at 20° C. (methanecontent of 0.01 vol %) was used as a model compound and passed into thehydrogen-storage tank to make the hydrogen gas react with thehydrogen-storage alloy to form a hydrogen-containing alloy. When thehydrogen-storage capacity of the hydrogen-storage alloy reached 75% ofthe theoretical capacity, the introduction of the hydrogen gascontaining organic substances was terminated, the purging with hydrogengas (purity: 95%) was performed for 20 minutes, then thehydrogen-storage tank was heated to keep the hydrogen-storage alloyunder 50 MPa to perform the continuous hydrogen release, and the purityof hydrogen gas was analyzed by gas chromatography. The purity ofhydrogen gas, the accumulated hydrogen-storage capacity and theattenuation rate of the hydrogen-storage capacity were shown in Table 3.The accumulated hydrogen-storage capacity refers to the total amount ofthe hydrogen gas absorbed in 30 runs of the hydrogen absorption. After30 runs of the above hydrogen absorption and hydrogen release cycle, theattenuation rate of the hydrogen-storage capacity was determined,wherein the attenuation rate=(the hydrogen-storage capacity at the firstrun of hydrogen absorption and hydrogen release minus thehydrogen-storage capacity at the 30th run of hydrogen absorption andhydrogen release)/the hydrogen-storage capacity at the first run ofhydrogen absorption and hydrogen release*100%.

Hydrogen-Storage Alloy Examples 14-26 and C5-C10

A total of about 1000g of metals according to the alloy composition wereweighed, placed in a water-cooled crucible of a vacuum induction meltingfurnace, and molten under vacuum to obtain an alloy, the preparationconditions including: the melting was performed under a backgroundvacuum of 1*10⁻⁴ Pa, and the melting temperature and time were shown inTable 3. The annealing was performed by lowering the temperature to theannealing temperature at a rate of 10° C./min under a background vacuumof 1*10⁻⁴ Pa, and the annealing temperature and time were shown in Table3. The nature cooling to room temperature was performed under abackground vacuum of 1*10⁻⁴ Pa. The obtained alloy was crushed andsieved to obtain 70-200 mesh metal powder. The powder was put into ahydrogen-storage tank, and the hydrogen-storage tank was heated to 300°C. under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder toobtain hydrogen-storage alloys 14-26 and C5-C10.

1 kg of hydrogen-storage alloy was placed in a hydrogen-storage tank,and a hydrogen gas containing organic substances at 10° C. (methanecontent of 0.05 vol %) was used as a model compound and passed into thehydrogen-storage tank to make the hydrogen gas react with thehydrogen-storage alloy to form a hydrogen-containing alloy. When thehydrogen-storage capacity of the hydrogen-storage alloy reached 75% ofthe theoretical capacity, the introduction of the hydrogen gascontaining organic substances was terminated, the purging with hydrogengas (purity: >98%) was performed for 20 minutes, then thehydrogen-storage tank was heated to keep the hydrogen-storage alloyunder 35 MPa to perform the continuous hydrogen release, and the purityof hydrogen gas was analyzed by gas chromatography. The purity ofhydrogen gas, the accumulated hydrogen-storage capacity and theattenuation rate of the hydrogen-storage capacity were shown in Table 3.The accumulated hydrogen-storage capacity refers to the total amount ofthe hydrogen gas absorbed in 10 runs of the hydrogen absorption. After10 runs of the above hydrogen absorption and hydrogen release cycle, theattenuation rate of the hydrogen-storage capacity was determined,wherein the attenuation rate=(the hydrogen-storage capacity at the firstrun of hydrogen absorption and hydrogen release minus thehydrogen-storage capacity at the 10th run of hydrogen absorption andhydrogen release)/the hydrogen-storage capacity at the first run ofhydrogen absorption and hydrogen release*100%.

Hydrogen-Storage Alloy Examples 27-40 and C11-C14

A total of about 1000g of metals according to the alloy composition wereweighed, placed in a water-cooled crucible of a vacuum induction meltingfurnace, and molten under vacuum to obtain an alloy, the preparationconditions including: the melting was performed under a backgroundvacuum of 1*10⁻⁴ Pa, and the melting temperature and time were shown inTable 3. The annealing was performed by lowering the temperature to theannealing temperature at a rate of 10° C./min under a background vacuumof 1*10⁻⁴ Pa, and the annealing temperature and time were shown in Table3. The nature cooling to room temperature was performed under abackground vacuum of I *10⁻⁴ Pa. The obtained alloy was crushed andsieved to obtain 70-200 mesh metal powder. The powder was put into ahydrogen-storage tank, and the hydrogen-storage tank was heated to 300°C. under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder toobtain hydrogen-storage alloys 27-40 and C11-C14.

1 kg of hydrogen-storage alloy was placed in a hydrogen-storage tank,and a hydrogen gas containing organic substances at 20° C. (methanecontent of 0.1 vol %) was used as a model compound and passed into thehydrogen-storage tank at a pressure of 5 MPa to make the hydrogen gasreact with the hydrogen-storage alloy to form a hydrogen-containingalloy.

When the hydrogen-storage capacity of the hydrogen-storage alloy reached75% of the theoretical capacity, the introduction of the hydrogen gascontaining organic substances was terminated, the purging with hydrogengas (purity: 95%) was performed for 20 minutes, then thehydrogen-storage tank was heated to keep the hydrogen-storage alloyunder 20 MPa to perform the continuous hydrogen release, and the purityof hydrogen gas was analyzed by gas chromatography. The purity ofhydrogen gas, the accumulated hydrogen-storage capacity and theattenuation rate of the hydrogen-storage capacity were shown in Table 3.The accumulated hydrogen-storage capacity refers to the total amount ofthe hydrogen gas absorbed in 10 runs of the hydrogen absorption. After10 runs of the above hydrogen absorption and hydrogen release cycle, theattenuation rate of the hydrogen-storage capacity was determined,wherein the attenuation rate=(the hydrogen-storage capacity at the firstrun of hydrogen absorption and hydrogen release minus thehydrogen-storage capacity at the 10th run of hydrogen absorption andhydrogen release)/the hydrogen-storage capacity at the first run ofhydrogen absorption and hydrogen release*100%.

Hydrogen-Storage Alloy Examples 41-56 and C 15-C 19

A total of about 1000 g of metals according to the alloy compositionwere weighed, placed in a water-cooled crucible of an arc-meltingfurnace, and molten under argon atmosphere to obtain an alloy, thespecific preparation including: the melting was performed under ahigh-purity Ar atmosphere (purity 99.999%), and the melting temperature,pressure and time were shown in Table 3. The annealing was performed bylowering the temperature to the annealing temperature of 650° C. at arate of 10° C./min under a background vacuum of 1*10⁻⁴ Pa. and for 48hours at that annealing temperature. The nature cooling to roomtemperature was performed under vacuum. The obtained alloy was crushedand sieved to obtain 70-200 mesh metal powder. The powder was put into ahydrogen-storage tank, and the hydrogen-storage tank was heated to 300°C. under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder toobtain hydrogen-storage alloys 41-56 and C15-C19. 1kg ofhydrogen-storage alloy was placed in a hydrogen-storage tank, and ahydrogen gas containing organic substances at 20° C. (methane content of0.1 vol %) was used as a model compound and passed into thehydrogen-storage tank at a pressure of 2 MPa to make the hydrogen gasreact with the hydrogen-storage alloy to form a hydrogen-containingalloy.

When the hydrogen-storage capacity of the hydrogen-storage alloy reached75% of the theoretical capacity, the introduction of the hydrogen gascontaining organic substances was terminated, the hydrogen-storage tankwas vacuumized with a vacuum pump at 80° C. for 5 minutes and thenheated to keep the hydrogen-storage alloy under 0.1 MPa to perform thecontinuous hydrogen release, and the purity of hydrogen gas was analyzedby gas chromatography. The purity of hydrogen gas, the accumulatedhydrogen-storage capacity and the attenuation rate of thehydrogen-storage capacity were shown in Table 3. The accumulatedhydrogen-storage capacity refers to the total amount of the hydrogen gasabsorbed in 10 runs of the hydrogen absorption. After 10 runs of theabove hydrogen absorption and hydrogen release cycle, the attenuationrate of the hydrogen-storage capacity was determined, wherein theattenuation rate=(the hydrogen-storage capacity at the first run ofhydrogen absorption and hydrogen release minus the hydrogen-storagecapacity at the 10th run of hydrogen absorption and hydrogenrelease)/the hydrogen-storage capacity at the first run of hydrogenabsorption and hydrogen release*100%.

Hydrogen-Storage Alloy Examples 57-67 and C20-C24

A total of about 1000 g of metals according to the alloy compositionwere weighed, placed in a water-cooled crucible of an arc-meltingfurnace, and molten under argon atmosphere to obtain an alloy, thespecific preparation including: the melting was performed under ahigh-purity Ar atmosphere (purity 99.999%1), and the meltingtemperature, pressure and time were shown in Table 3. The alloy wasnaturally cooled to room temperature under Ar atmosphere, thentransferred into a vacuum annealing furnace to perform the vacuumannealing under a background pressure of 1*10⁻⁴ Pa, wherein theannealing temperature and time were shown in Table 3; and naturallycooled to room temperature. The obtained alloy was crushed and sieved toobtain 70-200 mesh metal powder. The powder was put into ahydrogen-storage tank, and the hydrogen-storage tank was heated to50-300° C. under a vacuum of 0.1 Pa for 1-10 hours to activate the alloypowder (the specific activation temperature and time were shown in Table3) to obtain hydrogen-storage alloys 57-67 and C20-C24.

1kg of hydrogen-storage alloy was placed in a hydrogen-storage tank, anda hydrogen gas containing organic substances at 20° C. (methane contentof 0.1 vol %) was used as a model compound and passed into thehydrogen-storage tank at a pressure of 2 MPa to make the hydrogen gasreact with the hydrogen-storage alloy to form a hydrogen-containingalloy. When the hydrogen-storage capacity of the hydrogen-storage alloyreached 75% of the theoretical capacity, the introduction of thehydrogen gas containing organic substances was terminated, thehydrogen-storage tank was purged with hydrogen gas (purity 95%) for 20minutes and then heated to keep the hydrogen-storage alloy under 10 MPato perform the continuous hydrogen release, and the purity of hydrogengas was analyzed by gas chromatography. The purity of hydrogen gas wasshown in Table 3. After 10 runs of the above hydrogen absorption andhydrogen release cycle, the accumulated hydrogen-storage capacity andthe attenuation rate of the hydrogen-storage capacity were determined,and listed in Table 3, wherein the attenuation rate=(thehydrogen-storage capacity at the first run of hydrogen absorption andhydrogen release minus the hydrogen-storage capacity at the 10th run ofhydrogen absorption and hydrogen release)/the hydrogen-storage capacityat the first run of hydrogen absorption and hydrogen release*100%. Theaccumulated hydrogen-storage capacity refers to the total amount of thehydrogen gas absorbed in 10 runs of the hydrogen absorption.

The hydrogen-storage alloy provided by the present invention had goodresistance to organic substance pollution, had better hydrogenabsorption efficiency when the hydrogen gas contained organic substance,and had a higher hydrogen-storage capacity, and high-pressure andhigh-purity hydrogen gas could be obtained.

AB₅ Type Hydrogen-Storage Alloy Example 68

MmNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3), whereinMm=La_(0.61)Ce_(0.16)Pr_(0.04)Nd_(0.19)

A total of about 100g of metals according to the alloy composition wereweighed, placed in a water-cooled crucible of an arc-melting furnace,and molten under argon atmosphere to obtain an alloy, the preparationconditions including: high-purity Ar atmosphere (purity 99.999%),pressure 0.9-1.0 atm, electric current 80-200 A, voltage 40 V, meltingtime 10-60 minutes, natural cooling to room temperature, under the Aratmosphere. The alloy was transferred to high vacuum annealing furnacefor vacuum annealing, background pressure 1*10⁻⁴ Pa, annealingtemperature 800-950° C., annealing time 24-168 hours, and naturalcooling to room temperature. The obtained alloy was crushed and sievedto obtain 70-200 mesh metal powder. The powder was put into ahydrogen-storage tank, and the hydrogen-storage tank was heated to200-400° C. under a vacuum of 0.1 Pa for 1-4 hours to activate the alloypowder.

The following test methods were used to illustrate the effect of thecatalyst of Example 1 and the AB₅ type hydrogen-storage alloy of Example68 on the dehydrogenation reaction of the organic liquidhydrogen-storage material, and the separation by purification andpressurization.

The feedstock oil is methyl cyclohexane. The dehydrogenation reaction ofmethylcyclohexane was performed in a fixed bed microreactor for theevaluation, and the evaluation conditions were: reaction temperature350° C., pressure 1 MPa, make-up hydrogen flow rate 150 mL/minH2 (normalconditions), methylcyclohexane feedstock 2 mL/min, and catalyst loading20 g. The specific parameters and results were shown below

After the dehydrogenation reaction product was cooled, it was separatedin a separation tank placed in 20° C. brine, the cooling temperature wascontrolled to 20° C., the liquid product was collected, and the gasproduct was introduced into the hydrogen-storage alloy storage tank forthe hydrogen absorption. After the adsorption capacity of thehydrogen-storage alloy reached the set value, the hydrogen-storage alloystorage tank was purged with hydrogen with purity of 99% at the hydrogenabsorption temperature for 30 minutes, and then the hydrogen-storagealloy was heated to release the hydrogen gas.

wherein, the conversion rate=reacted methylcyclohexane/totalmethylcyclohexane feed

The reaction products were analyzed by chromatography, and theconversion rate was calculated using the product composition data at the10th minute.

Dehydrogenation reaction temperature: 350° C.

Dehydrogenation reaction pressure: 1 MPa

Organic liquid dehydrogenation conversion rate: 98.50%

Hydrogen absorption temperature: 20° C.

Hydrogen partial pressure for hydrogen absorption: 0.2 MPa

Hydrogen release temperature: 200° C.

Hydrogen partial pressure for hydrogen release: 35 MPa

Purity of hydrogen gas: 99.99%

Hydrogen-storage capacity (200 mL): 14.1 g.

TABLE 1 Support preparation conditions, support composition and supportproperties Shift at Shift at 458.8eV 464,5eV of Ti 2P_(3/2) of Ti2P_(1/2) orbital orbital Modified support Specific Pore electronelectron Support Support composition, wt % Fluidization Hydrolysissurface volume binding binding Example Name Al₂O₃ TiO₂ ZrO₂ time/hourstime/hours area/cm2/g mL/g μ θ energy, eV energy, eV 1 1 97.02 2.98 1 4174 0.48 0 33.2 0.63 0.82 2 2 94.23 5.77 2 8 170 0.48 0 16.6 0.63 0.82 33 92.11 7.89 3 10 168 0.46 0 12.0 0.63 0.82 4 4 90.03 9.97 4 16 165 0.450 9.3 0.62 0.81 5 5 88.22 11.78 5 18 164 0.45 0 7.8 0.62 0.81 6 6 86.4713.53 6 20 162 0.43 0 6.8 0.62 0.81 7 7 84.8 15.2 7 25 161 0.43 0 6.00.61 0.80 8 8 83.3 16.7 8 30 160 0.42 0 5.4 0.61 0.80 9 9 95.79 2.861.35 1 8 172 0.47 0 34.3 0.63 0.82 10 10 89.27 7.25 3.48 3 16 167 0.45 012.8 0.62 0.82 11 11 83.18 11.59 5.23 5 30 160 0.42 0 7.8 0.61 0.81Comparative 1 C1 100 176 0.48 Comparative 2 C2 97.08 2.92 172 0.43 0.41.6 0 0 Comparative 3 C3 90.12 9.88 163 0.42 0.5 1.5 0 0 Comparative 4C4 86.55 13.45 150 0.4 0.5 2.4 0.41 0.52 Comparative 5 C5 86.58 13.42150 0.4 0.5 2.6 0.41 0.53 Comparative 6 C6 95.75 2.88 1.37 169 0.43 0.41.4 0 0 Comparative 7 C7 83.24 11.51 5.25 151 0.39 0.5 1.1 0 0 Note: Thesupport composition was the normalized result of the XRF measurement.

TABLE 2 Chloro- Hydrogen platinic Nickel Methyl- gas Support acidnitrate Other metal cyclohexane generation Weight Weight Weight Weightconversion rate^([a]) microreaction Example Names (wt %) (wt %) (wt %)Names (wt %) rate Selectivity yield mL\h test condition^([b]) 1 1 99.20.8 76.90% 98.40% 0.76 48.06 350, 150, 2 2 1 99.4 0.6 70.20% 98.60% 0.6943.98 350, 150, 2 3 1 99.4 0.6 74.10% 98.70% 0.73 46.4 350, 150, 2 4 196.5 0.5 1 copper nitrale 2 73.20% 97.90% 0.72 56.94 350, 150, 2.5 5 198.5 0.5 1 72.10% 97.30% 0.70 55.95 350, 150, 2.5 6 1 98.5 0.5 1 73.20%97.40% 0.71 56.72 350, 150, 2.5 7 1 99.5 0.5 62.80% 98.40% 0.62 49.03350, 150, 2.5 8 1 90 10 76.90% 99.00% 0.76 96.53 350, 300, 4 9 1 98 272.80% 98.80% 0.72 91.77 350, 300, 4 10 I 88 10 tin chloride 2 95.60%91.80% 0.88 28.49 400, 150, 1.0 11 1 88 10 tin chloride 2 96.00% 92.10%0.88 28.72 400, 150, 1.0 12 1 90 10 93.50% 90.50% 0.85 27.57 400, 150,1.0 13 2 98.9 palladium 0.6 70.80% 95.60% 0.68 43.44 350, 150, 2chloride chloroiridic 0.5 acid 14 2 99.2 0.6 rhenium 0.2 76.10% 98.50%0.75 47.62 350,150, 2 trichloride 15 2 91.7 0.3 8 68.40% 93.60% 0.6451.5 350, 150, 2.5 16 2 75 10 iron nitrate 9 95.80% 82.40% 0.79 26.65400, 150, 1.0 ammonium 6 phosphate 17 3 99.2 0.6 palladium 0.2 76.50%98.60% 0.75 47.88 350, 150, 2 chloride 18 3 99.2 0.6 palladium 0.276.50% 98.60% 0.75 47.88 350, 150, 2 chloride 19 3 84.9 0.1 15 63.50%90.40% 0.57 46.64 350, 150, 2,5 20 3 89 8 tin chloride 1 95.40% 91.20%0.87 28.27 400,150, 1.0 zinc nitrate 2 21 4 98.9 0.6 chloroiridic 0.577.00% 95.80% 0.74 47.25 350, 150, 2 acid 22 4 87 9 iron nitrate 495.20% 87.80% 0.84 27.59 400, 150, 1.0 23 5 96.4 0.6 tin chloride 376.20% 97.20% 0.74 47.28 350, 150, 2 24 5 96.5 0.5 tin chloride 3 68.20%97.20% 0.66 52.81 350, 150, 2.5 25 5 85 10 silver nitrate 5 95.00%90.20% 0.86 27.92 400, 150, 1.0 26 6 94.4 0.6 5 nickel nitrate 76.50%96.30% 0.74 47.1 350, 150, 2 27 6 99.2 0.8 76.60% 98.20% 0.75 47.81 350,150, 2 28 6 88.7 0.3 8 tin chloride 3 70.80% 94.20% 0.67 53.58 350, 150,2.5 29 6 87 8 zinc nitrate 3 95.90% 97.10% 0.88 28.6 400, 150, 1.0copper nitrate 2 30 7 86 8 zinc nitrate 3 95.80% 89.80% 0.86 28.17 400,150, 1.0 iron nitrate 3 31 9 94.4 0.6 manganous 5 76.60% 95.10% 0.7346.81 350, 150, 2 nitrate 32 9 99.2 0.8 76.50% 98.10% 0.75 47.71 350,150, 2 33 9 94.5 0.5 manganous 5 62.60% 93.70% 0.59 46.99 350, 150, 2.5nitrate 34 9 88 10 zinc nitrate 2 95.10% 90.50% 0.86 28.07 400, 150, 1.035 10 93.4 0.6 copper nitrate 6 76.70% 96.50% 0.74 47.33 350, 150, 2 3610 99.2 0.8 76.70% 98.50% 0.76 47.96 350, 150, 2 37 10 93.5 0.5 coppernitrate 6 64.80% 96.50% 0.63 49.9 350, 150, 2.5 38 10 92 6 coppernitrate 2 94.50% 90.60% 0.86 27.95 400, 150, 1.0 39 11 79.9 0.1 15manganous 5 66.90% 92.30% 0.62 49.79 350, 150, 2.5 nitrate ComparativeC1 99.2 0.6 rhenium 0.2 66.00% 98.00% 0.65 41.32 350, 150, 2 1trichloride Comparative C1 99.5 0.5 58.50% 98.10% 0.57 45.51 350, 150,2.5 2 Comparative C1 88 10 tin chloride 2 80.10% 91.10% 0.73 23.72 400,150, 1.0 3 Comparative C2 99.2 0.8 67.00% 97.80% 0.66 41.7 350, 150, 2 4Comparative C2 96.5 0.5 1 copper nitrate 2 61.80% 96.70% 0.60 47.63 350,150, 2.5 5 Comparative C2 98.5 0.5 1 59.50% 97.60% 0.58 46. 17 350, 150,2.5 6 Comparative C2 88 10 tin chloride 2 83.20% 91.70% 0.76 24.79 400,150, 1.0 7 Comparative C3 98.9 0.6 chloroiridic 0.5 62.60% 95.00% 0.5938.23 350, 150, 2 8 acid Comparative C3 87 9 iron nitrate 4 86.20%87.20% 0.75 24.8 400, 150, 1.0 9 Comparative C4 94.4 0.6 5 nickelnitrate 64.50% 91.80% 0.59 38.51 350, 150, 2 10 Comparative C4 99.2 0.864.50% 96.80% 0.62 39.86 350, 150, 2 11 Comparative C5 99.2 0.8 65.80%97.30% 0.64 40.81 350, 150, 2 12 Comparative C5 88.7 0.3 8 tin chloride3 54.80% 90.20% 0.49 40.14 350, 150, 2.5 13 Comparative C5 87 8 zincnitrate 3 90.80% 91.90% 0.83 27.04 400, 150, 1.0 14 copper nitrate 2Comparative C6 94.4 0.6 manganous 5 60.30% 93.80% 0.57 36.55 350, 150, 215 nitrate Comparative C6 94.5 0.5 manganous 5 57.30% 93.80% 0.54 43.25350, 150, 2.5 16 nitrate Comparative C6 88 10 zinc nitrate 2 75.60%91.80% 0.69 22.52 400, 150, 1.0 17 Note^([a]): The hydrogen generationrate in the above Table does not include the supplementary hydrogen inthe feed. Note^([b]): Micro reaction test conditions: temperature° C.,make-up hydrogen flow rate (mL/minH2), methylcyclohexane feed rate(mL/min)

TABLE 3 Hydrogen- Melting storage temper- Melting Melting AnnealingActivation alloy, ature, time, pressure, temper- Annealing, temper-Example ° C. hour bar ature, ° C. time, hours ature, ° C. 1 800 1 800 242 1850 0.8 920 60 3 1950 0.7 850 90 4 2040 0.5 900 115 5 2100 0.3 840134 6 2200 0.2 950 168 7 1800 1 800 24 8 1850 0.8 920 60 9 1950 0.7 85090 10 2040 0.5 900 115 11 2100 0.3 840 134 12 2200 0.2 950 168 13 19500.7 850 90 C1 1800 1 800 24 C2 1850 0.8 920 60 C3 2040 0.5 900 115 C42100 0.3 840 134 14 2200 1 950 24 15 1870 0.9 930 65 16 2000 0.7 900 9017 2050 0.6 880 120 18 2130 0.4 85 142 19 2200 0.2 800 168 20 2200 1 95024 21 1870 0.9 930 65 22 2000 0.7 900 90 23 2050 0.6 880 120 24 2130 0.485 142 25 2200 0.2 800 168 26 2200 1 950 24 C5 2200 1 950 24 C6 1870 0.9930 65 C7 2000 0.7 900 90 C8 2050 0.6 880 120 C9 2130 0.4 85 142 C102200 0.2 800 168 27 1850 0.8 800 98 28 1950 1 750 180 29 1830 0.5 980 8030 2200 1.5 840 240 31 2040 2 780 120 37 1850 1.5 980 80 33 1950 2 750180 34 1850 0.8 800 98 35 1950 1 750 180 36 1830 0.5 980 80 37 2200 1.5840 240 38 2040 2 780 120 39 1850 1.5 980 80 40 1950 2 750 180 C11 18500.8 800 98 C12 1950 1 750 180 C13 1830 0.5 980 80 C14 2200 1.5 840 24041 1850 0.8 0.6 650 48 42 1950 1 0.9 650 48 43 1830 0.5 0.8 650 48 442200 1.5 1 650 48 45 2040 2 0.7 650 48 46 1850 1.5 0.9 650 48 47 1950 20.7 650 48 48 2040 0.8 1 650 48 49 1850 0.8 0.6 650 48 50 1950 1 0.9 65048 51 1830 0.5 0.8 650 48 52 2200 1.5 1 650 48 53 2040 2 0.7 650 48 541850 1.5 0.9 650 48 55 1950 2 0.7 650 48 56 2040 0.8 1 650 48 C15 18500.8 0.6 650 48 C16 1950 1 0.9 650 48 C17 1830 0.5 0.8 650 48 C18 22001.5 1 650 48 C19 2040 2 0.7 650 48 57 1850 0.8 0.6 800 98 80 58 1950 10.9 750 180 100 59 1830 0.5 0.8 980 80 95 60 2200 1.5 1 840 240 240 612040 2 0.7 780 120 180 62 1850 0.8 0.6 800 98 80 63 1950 1 0.9 750 180100 64 1830 0.5 0.8 980 80 95 65 2200 1.5 1 840 240 240 66 2040 2 0.7780 120 180 67 1850 0.8 0.6 800 98 80 C20 1850 0.8 0.6 800 98 80 C211950 1 0.9 750 180 100 C22 1830 0.5 0.8 980 80 95 C23 2200 1.5 1 840 240240 C24 2040 2 0.7 780 120 180 Hydrogen- Accumulated storage hydrogen-alloy, Activation storage Hydrogen Attenuation Example time, hoursHydrogen-storage alloy formula capacity, g purity, % rate, % 1(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05) 581.28 ≥99.95 1.27 2(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1) 582.29≥99.95 0.92 3 (Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1)582.46 ≥99.95 0.87 4(Ti_(0.4).Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07)582.63 ≥99.95 0.81 5(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05)581.54 ≥99.95 1.18 6(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05)583.31 ≥99.95 0.58 7 (Ti_(0.8)V_(0.2))_(0.95)(Fe₁)_(0.05) 580.61 ≥99.951.5 8 (Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.95))_(0.1) 581.45≥99.95 1.21 9 (Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn₁)_(0.1) 581.77 ≥99.951.1 10 (Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Co_(0.1))_(0.07)581.87 ≥99.95 1.07 11(Ti_(0.4)V_(0.4)Zr_(0.2))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05)580.94 ≥99.95 1.39 12(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Co_(0.1))_(0.05)582.8 ≥99.95 0.75 13 (Ti0.7Nb0.1Y0.2)0.8(Mn0.7Ni0.3)0.2 579.02 ≥99.952.04 C1 Ti_(0.8)V_(0.2))_(0.95)(Mn_(0.55)Ni_(0.45))_(0.05) 564.28 99.687 C2 (Nb_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1)557.85 99.74 9.14 C3(V_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Co_(0.1))_(0.07) 566.8899.79 6.13 C4(Ti_(0.4)V_(0.4)Zr_(0.2))_(0.95)(Fe_(0.5)Mn_(0.2)Co_(0.3)Ni_(0.45))_(0.05)568.27 99.86 5.67 14Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1) 134.27 ≥99.97 1.0715Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.5)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1)134.65 ≥99.97 0.52 16Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2) 134.59≥99.97 0.6 17Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05)V_(1.21)Mn_(0.6)Ni_(0.1)Cu_(0.2)134.3 ≥99.97 1.03 18Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2)134.67 ≥99.97 0.49 19Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1))Cu_(0.1)134.61 ≥99.97 0.58 20 Ti_(0.64)Zr_(0.45)Y_(0.01)VMn_(0.9)Ni_(0.1) 134.24≥99.97 1.12 21Ti_(0.55)Zr_(0.48)Y_(0.05)La_(0.02)V_(0.33)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)134.57 ≥99.97 0.64 22 Ti_(0.6)Zr_(0.4)Y_(0.05)V_(0.1)Mn_(1.8)Ni_(0.2)134.44 ≥99.97 0.83 23Ca_(0.01)Ti_(0.9)Zr_(0.5)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.3) 134.15 ≥99.971.25 24 TiZr_(0.05)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.3)134.47 ≥99.97 0.78 25Ti_(0.5)Zr_(0.55)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.2) 134.43 ≥99.970.84 26 Mg_(0.01)Ti_(0.63)Zr_(0.45)Y_(0.01)VMn_(0.9)Ni_(0.1) 133.97≥99.97 1.52 C5 Ti_(0.65)Zr_(0.45)VMn_(0.9)Ni_(0.1) 130.77 99.72 6.21 C6Ti_(1.03)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1)131.83 99.85 4.67 C7Mg_(0.5)Zr_(0.5)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2) 131.3 99.79 5.44C8 Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.7)Cu_(0.2) 130.9499.74 5.96 C9Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.3)Cr_(1.4)Co_(0.1)Ni_(0.1)Cu_(0.2)132.71 99.89 3.38 C10Ti_(0.8)Zr_(0.25)Y_(0.05)Mn_(1.89)Fe_(0.01)Ni_(0.1)Cu_(0.1) 132.12 99.864.25 27 TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1) 139.22 ≥99.97 0.4 28TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1) 139.17 ≥99.97 0.47 29Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4) 139.31 ≥99.97 0.27 30Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1) 139.4 ≥99.97 0.04 31Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1) 139.44 ≥99.970.09 37 Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05) 139.01≥99.97 0.7 33 Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1) 139.24≥99.97 0.38 34 TiY_(0.01)V_(0.1)Fe_(0.7)Ni_(0.2) 139.06 ≥99.97 0.63 35TiY_(0.02)V_(0.2)Fe_(0.8) 138.99 ≥99.97 0.73 36Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.9) 139.2 ≥99.97 0.43 37Ti_(0.9)Y_(0.04)V_(0.15)Fe_(0.9) 139.44 ≥99.97 0.09 38Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.7) 139.36 ≥99.97 0.21 39Ti_(0.95)Y_(0.05)V_(0.26)Fe_(0.7)Cu_(0.05) 138.75 ≥99.97 1.07 40Ti_(0.2)Y_(0.03)V_(0.05)Fe_(0.9)Ni_(0.1) 139 ≥99.97 0.72 C11TiV_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1) 135.31 99.63 5.96 C12TiY_(0.02)Fe_(0.9)Mn_(0.1) 134.88 99.54 6.55 C13TiV_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4) 135.55 99.75 5.61 C14Ti_(0.9)Y_(0.04)Fe_(0.95)Mn_(0.1) 136.95 99.89 3.63 41Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁ 267.34 ≥99.99 1.96 42Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁ 268.43 ≥99.99 1.16 43Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4) 268.79 ≥99.99 0.9 44Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05) 269.03 ≥99.99 0.72 45Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1) 769.24 ≥99.99 0.57 46Mg_(1.9)Y_(0.1)C_(r0.1)Ni_(0.8)Co_(0.2) 269.42 ≥99.99 0.43 47Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1) 269.45 ≥99.99 0.4 48Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3) 268.91 ≥99.99 0.81 49Mg_(1.8)Y_(0.1)Ni₁ 266.62 ≥99.99 2.49 50Mg_(1.5)Ti_(0.5)Y_(0.05)Ni_(1.1) 267.82 ≥99.99 1.61 51Mg₂Y_(0.1)Ni_(0.6)Cu_(0.4) 268.18 ≥99.99 1.34 52Mg_(1.92)Y_(0.08)Ni_(0.95)Fe_(0.05) 268.49 ≥99.99 1.12 53Mg_(1.9)Y_(0.1)Fe_(0.1)Ni_(0.8)Cu_(0.1) 268.73 ≥99.99 0.94 54Mg_(1.9)Y_(0.1)Ni_(0.8)Co_(0.2) 268.93 ≥99.99 0.79 55Mg_(1.8)Y_(0.1)La_(0.1)Ni_(0.9)Co_(0.1) 269.02 ≥99.99 0.73 56Mg_(1.7)Ti_(0.2)Y_(0.1)Ni_(0.7)Co_(0.32) 268.63 ≥99.99 1.01 C15Mg_(1.9)Ni₁ 258.4 99.43 8.48 C16 Mg_(1.5)Ti_(0.5)Ni_(1.1) 259.9 99.557.39 C17 Mg_(2.1)Ni_(0.6)Cu_(0.4) 260.67 99.63 6.84 C18Mg₂Ni_(0.95)Fe_(0.05) 262.71 99.68 5.36 C19 Mg₂Fe_(0.1)Ni_(0.8)Cu_(0.1)263.89 99.76 4.5 57 7La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.55)Al_(0.05)104.75 ≥99.97 0.48 58 6 La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5)104.9 ≥99.97 0.2 59 5La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2) 104.86≥99.97 0.27 60 8La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2)104.98 ≥99.97 0.04 61 4La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1)104.95 ≥99.97 0.09 62 7La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.6) 104.63≥99.97 0.7 63 6 La_(0.8)Ce_(0.15)Y_(0.05)Ni_(4.5)Mn_(0.5) 104.8 ≥99.970.38 64 5 La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni_(4.2)Co_(0.8)104.76 ≥99.97 0.45 65 8La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.8)Fe_(0.2) 104.95≥99.97 0.09 66 4La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.4)Mn_(0.1) 104.86 ≥99.970.27 67 7 La_(0.97)Y_(0.03)Ni₄Co₁ 104.39 ≥99.97 1.16 C20 7La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.03)Ni_(4.4)Fe_(0.6) 101.39 99.76 6.8 C216 La_(0.8)Ce_(0.2)Ni_(4.5)Mn_(0.5) 102.07 99.83 5.53 C22 5La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.05)Ni_(4.2)Co_(0.8) 101.89 99.56 5.87 C238 La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.05)Ni_(4.8)Fe_(0.2) 102.62 99.85 4.5C24 4 La_(0.8)Ce_(0.15)Nd_(0.05)Ni_(4.5)Co_(0.4)Mn_(0.1) 102.12 99.895.44

1. A hydrogen-storage alloy, wherein the hydrogen-storage alloy is oneor more of rare earth-based AB₅ type, zirconium-titanium-based AB₂ type,titanium-based AB type, magnesium-based A₂B type and vanadium-basedsolid solution type hydrogen-storage alloys, wherein The molecularformula of the rare earth-based AB₅ type hydrogen-storage alloy is:M_(m)Ni_(x1)Co_(x2)Mn_(x3)Fe_(x4)Al_(x5)Sn_(x6), 4.5

x1+x2+x3+x4+x5+x6

5.5, wherein, M_(m) is La_(y1)Ce_(y2)Nd_(y3)Pr_(y4)Y_(y5),y1+y2+y3+y4+y5=1, wherein, 0.4

y1

0.99 (e.g., 0.4

y1

0.8), 0

y2

0.45 (e.g., 0.1

y2

0.45), 0

y3

0.2 (e.g., 0

y3

0.2), 0

y4

0.05 (e.g., 0

y4

0.05), 0.01

y5

0.1 (e.g., 0.01

y5

0.05), 3

x1

5.45 (e.g., 3

x1

4.9), 0

x2

1.5 (e.g., 0.1

x2

1), 0

x3

0.8 (e.g., 0.1

x3

0.6), 0

x4

0.8 (e.g., 0.1

x4

0.6), 0

x5

0.75 (e.g., 0.05

x5

0.5), 0

x6

0.2; (e.g., 0

x6

0.15); The molecular formula of the zirconium-titanium-based AB₂ typehydrogen-storage alloy is AB₂, whereinA=Mg_(x1)Cax2Ti_(x3)Zr_(x4)Y_(x5)La_(x6), x1+x2+x3+x4+x5+x6=0.9-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=1.9-2.1, 0

x1

0.54 (e.g., 0.01

x1

0.3, 0.01

x1

0.1), 0

x2

0.54 (e.g., 0

x2

0.25), 0.5

x3

1.04 (e.g., 0.6

x3

1), 0.05

x4

0.58 (e.g., 0.1

x4

0.58), 0.01

x5

0.2 (e.g., 0.01

x5

0.05), 0

x6

0.2 (e.g., 0

x6

0.05), 0.05

y1

1.95 (e.g., 0.05

y1

1.8), 0

y2

1.9 (e.g., 0

y2

1.85), 0.05

y3

1.95 (e.g., 0.1

y3

1.95), 0

y4

1.6 (e.g., 0

y4

1.5), 0

y5

0.5 (e.g., 0

y5

0.3), 0.1

y6

0.5 (e.g., 0.1

y6

0.3), 0

y7

0.5 (e.g., 0.1

y7

0.2), preferably, 0.7

x3:(x3+x4)

0.95, preferably, 1.7

y1+y2+y3+y4

2; The molecular formula of the titanium-based AB type hydrogen-storagealloy is AB, wherein A=Ti_(x1)Zr_(x2)Y_(x3)La_(x4),x1+x2+x3+x4=0.85-1.1,B=V_(y1)Cr_(y2)Mn_(y3)Fe_(y4)Co_(y5)Ni_(y6)Cu_(y7),y1+y2+y3+y4+y5+y6+y7=0.95-1.05, 0

x1

1.09 (e.g., 0.9

x1

1.05), 0

x2

1.09 (e.g., 0

x2

0.5), 0.01

x3

0.2 (e.g., 0.01

x3

0.05), 0

x4

0.2 (e.g., 0

x4

0.05), 0.05

y1

0.5 (e.g., 0.05

y1

0.2), 0

y2

0.8 (e.g., 0

y2

0.2), 0

y3

0.8 (e.g., 0.05

y3

0.4, or 0.1

y3

0.4), 0.2

y4

1 (e.g., 0.5

y4

0.9), 0

y5

0.35 (e.g., 0

y5

0.1), 0

y6

0.45 (e.g., 0

y6

0.2), 0

y7

0.3 (e.g., 0

y7

0.2), preferably, x1 and x2 are zero at the same time; The molecularformula of the magnesium-based A₂B type hydrogen-storage alloy is A₂B,wherein A=Mg_(x1)Ca_(x2)Ti_(x3)La_(x4)Y_(x5), x1+x2+x3+x4+x5=1.9-2.1,B=Cr_(y1)Fe_(y2)Co_(y3)Ni_(y4)Cu_(y5)Mo_(y6); y1+y2+y3+y4+y5+y6=0.9-1.1;wherein, 1.29

x1

2.09 (e.g., 1.7

x1

2.05), 0

x2

0.5 (e.g., 0

x2

0.2), 0

x3

0.8 (e.g., 0

x3

0.5), 0

x4

0.5 (e.g., 0

x4

0.2), 0.01

x5

0.2 (e.g., 0.05

x5

0.1), 0

y1

0.3 (e.g., 0

y1

0.2, 0.05

y1

0.2), 0

y2

0.2 (e.g., 0

y2

0.1), 0

y3

0.6 (e.g., 0

y3

0.5), 0.2

y4

1.1 (e.g., 0.7

y4

1.05), 0

y5

0.5 (e.g., 0

y5

0.4), 0

y6

0.15 (e.g., 0

y6

0.1); The molecular formula of the vanadium-based solid solution typehydrogen-storage alloy is A_(x1)B_(x2), wherein x1+x2=1, whereinA=Ti_(y1)V_(y2)Zr_(y3)Nb_(y4)Y_(y5)La_(y6)Ca_(y7),y1+y2+y3+y4+y5+y6+y7=1, B=Mn_(z1)Fe_(z2)Co_(z3)Ni_(z4), z1+z2+z3+z4=1,0.7

x1

0.95 (e.g., 0.8

x1

0.95, 0.9

x1

0.95), 0.05

x2

0.3 (e.g., 0.05

x2

0.2, 0.05

x2

0.1), 0.40

y1

0.9 (e.g., 0.45

y1

0.9, 0.5

y1

0.8), 0

y2

0.5 (e.g., 0

y2

0.4), 0

y3

0.5 (e.g., 0

y3

0.4), 0

y4

0.55 (e.g., 0

y4

0.4), 0

y5

0.2 (e.g., 0.01

y5

0.2, 0.05

y5

0.2), 0

y6

0.1 (e.g., 0

y6

0.05), 0

y7

0.1 (e.g., 0

y7

0.05), 0

z1

1 (e.g., 0.1

z1

1, 0.2

z1

0.95), 0

z2

0.95 (e.g., 0

z2

0.9), 0

z3

0.3 (e.g., 0

z3

0.2), 0

z4

0.45 (e.g., 0.05

z4

0.45, 0.05

z4

0.3), 0.55

z1+z2

1 (e.g., 0.7

z1+z2

1).
 2. The hydrogen-storage alloy according to claim 1, wherein thehydrogen-storage alloy is selected from: La_(0.61)Ce_(0.16)Pr₄Nd_(0.19)Ni_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3),(Ti_(0.8)V_(0.2))_(0.95)(Fe₁)_(0.05),(Ti_(0.8)Y_(0.2))_(0.95)(Mn_(0.95)Ni_(0.05))_(0.05),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.95))_(0.1),(Ti_(0.4)V_(0.4)Y_(0.2))_(0.9)(Fe_(0.05)Mn_(0.9)Ni_(0.05))_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn₁)_(0.1),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.9)(Mn_(0.7)Ni_(0.3))_(0.1),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Co_(0.1))_(0.07),(Ti_(0.4)Zr_(0.4)Y_(0.2))_(0.93)(Fe_(0.2)Mn_(0.7)Ni_(0.1))_(0.07),(Ti_(0.4)V_(0.4)Zr_(0.2))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.4)V_(0.35)Zr_(0.2)Y_(0.05))_(0.95)(Fe_(0.6)Mn_(0.2)Co_(0.1)Ni_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Co_(0.1))_(0.05),(Ti_(0.88)Y_(0.1)Ca_(0.02))_(0.95)(Fe_(0.3)Mn_(0.6)Ni_(0.1))_(0.05),(Ti_(0.7)Nb_(0.1)Y_(0.2))_(0.8)(Mn_(0.7)Ni_(0.3))_(0.2),Ti_(0.64)Zr0.45Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(0.01)Ti_(0.93)Zr_(0.15)Y_(0.01)VMn_(0.9)Ni_(0.1),Ti_(0.55)Zr_(0.48)Y_(0.05)La_(0.02)V_(0.33)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1),Ti_(0.85)Zr_(0.18)Y_(0.05)La_(0.02)V_(0.23)Cr_(0.05)Mn_(1.5)Fe_(0.09)Ni_(0.1)Cu_(0.1),Ti_(0.6)Zr_(0.4)Y_(0.05)V_(0.1)Mn_(1.8)Ni_(0.2),Mg_(0.1)Ti_(0.7)Zr_(0.2)Y_(0.05)V_(0.1)Mn_(1.6)Ni_(0.2)Cu_(0.2),Ca_(0.01)Ti_(0.9)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.3),Ca_(0.01)Ti_(0.85)Zr_(0.05)Y_(0.05)V_(1.2)Mn_(0.6)Ni_(0.1)Cu_(0.2),TiZr_(0.05)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.3),Mg_(0.1)Ti_(0.8)Zr_(0.15)Y_(0.05)V_(0.1)Cr_(1.4)Mn_(0.2)Co_(0.1)Ni_(0.1)Cu_(0.2),Ti_(0.5)Zr_(0.55)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.2),Ti_(0.8)Zr_(0.25)Y_(0.05)V_(1.79)Mn_(0.1)Fe_(0.01)Ni_(0.1)Cu_(0.1),Mg_(0.01)Ti_(0.63)Zr_(0.45)Y_(0.01)VMn_(0.9)Ni_(0.1),Mg_(1.8)Y_(0.1)Ni₁, Mg_(1.8)Y_(0.1)Cr_(0.05)Ni₁,Mg_(1.5)Ti_(0.5)Y_(0.05)Ni_(1.1), Mg_(1.5)Ti_(0.5)Y_(0.05)Cr_(0.1)Ni₁,Mg₂Y_(0.1)Ni_(0.6)Cu_(0.4), Mg₂Y_(0.1)Cr_(0.05)Ni_(0.6)Cu_(0.4),Mg_(1.92)Y_(0.08)Ni_(0.95)Fe_(0.05),Mg_(1.92)Y_(0.08)Cr_(0.2)Ni_(0.75)Fe_(0.05),Mg_(1.9)Y_(0.1)Fe_(0.1)Ni_(0.8)Cu_(0.1),Mg_(1.9)Y_(0.1)Cr_(0.1)Fe_(0.1)Ni_(0.7)Cu_(0.1),Mg_(1.9)Y_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.9)Y_(0.1)Cr_(0.1)Ni_(0.8)Co_(0.2), Mg_(1.8)Y_(0.1)La_(0.1)Ni_(0.9)Co_(0.1), Mg_(1.8)Y_(0.1)La_(0.1)Cr_(0.05)Ni_(0.9)Co_(0.1),Mg_(1.7)Ti_(0.2)Y_(0.1)Ni_(0.7)Co_(0.32),Mg_(1.7)Ti_(0.2)Y_(0.1)Cr_(0.05)Ni_(0.7)Co_(0.3),TiY_(0.01)V_(0.1)Fe_(0.7)Ni_(0.2),TiY_(0.01)V_(0.1)Fe_(0.7)Mn_(0.1)Ni_(0.1), TiY_(0.02)V_(0.2)Fe_(0.8),TiY_(0.02)V_(0.2)Fe_(0.7)Mn_(0.1),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.9),Ti_(0.97)Y_(0.03)V_(0.05)Cr_(0.03)Fe_(0.5)Mn_(0.4),Ti_(0.9)Y_(0.04)V_(0.15)Fe_(0.9),Ti_(0.9)Y_(0.04)V_(0.05)Fe_(0.9)Mn_(0.1),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.7),Ti_(0.91)Zr_(0.05)Y_(0.04)V_(0.1)Cr_(0.2)Fe_(0.6)Mn_(0.1),Ti_(0.95)Y_(0.05)V_(0.26)Fe_(0.7)Cu_(0.05), Ti_(0.95)Y_(0.05)V_(0.05)Fe_(0.7)Mn_(0.21)Cu_(0.05),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.9)Ni_(0.1),Ti_(1.02)Y_(0.03)V_(0.05)Fe_(0.8)Mn_(0.1)Ni_(0.1),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.55)Al_(0.05),La_(0.5)Ce_(0.32)Nd_(0.15)Pr_(0.02)Y_(0.01)Ni_(4.4)Fe_(0.6),La_(0.8)Ce_(0.15)Y_(0.05)Ni₄Mn_(0.5)Al_(0.5),La_(0.8)Ce_(0.15)Y_(0.05)Ni_(4.5)Mn_(0.5),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni₄Co_(0.8)Al_(0.2),La_(0.45)Ce_(0.4)Nd_(0.1)Pr_(0.03)Y_(0.02)Ni_(4.2)Co_(0.8),La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.7)Al_(0.1)Fe_(0.2),La_(0.75)Ce_(0.15)Nd_(0.05)Pr_(0.02)Y_(0.03)Ni_(4.8)Fe_(0.2),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.3)Mn_(0.1)Al_(0.1),La_(0.8)Ce_(0.15)Nd_(0.03)Y_(0.02)Ni_(4.5)Co_(0.4)Mn_(0.1),La_(0.97)Y_(0.03)Ni₄Co₁.
 3. The process for preparing thehydrogen-storage alloy according to claim 1, wherein thehydrogen-storage alloy is prepared by the following process, whichcomprises the following steps: (1) weighing each of the raw materials ofthe hydrogen-storage alloy in a way to reach the composition of thehydrogen-storage alloy and mixing the raw materials; (2) melting themixture obtained in step (1) and then annealing; Wherein the melting iselectric furnace melting or induction melting; Preferably, the meltingcondition comprises: it is performed under vacuum or inert atmosphere,the temperature is 1200-3000° C., preferably 1800-2200° C.; Morepreferably, it is performed under vacuum, and the melting pressure is1*10⁻⁵ to 1*10⁻³ Pa (absolute pressure), preferably 0.5*10⁻⁴ to 5*10⁻⁴Pa (absolute pressure); More preferably, it is performed under inertatmosphere, and the melting pressure is 0.5-1 bar (for example, 0.6-1bar, 0.7-1 bar) (gauge pressure), Wherein the annealing conditioncomprises: it is performed under vacuum or inert atmosphere (e.g., argonatmosphere), the temperature is 500-900° C. (for example 700-1000° C.),the time is 12-360 hours; Optionally, the process further comprisescooling the material obtained by annealing in step (2) and thenperforming a crushing treatment to obtain a product of 10-400 mesh (forexample, 20-400 mesh), Optionally, the process further comprisessubjecting the material obtained by annealing in step (2) to activationtreatment; preferably, the condition of the activation treatmentcomprises: it is performed under vacuum, the temperature is 50-300° C.,and the time is 1-10 hours.
 4. Use of the hydrogen-storage alloyaccording to claim 1 in the hydrogen-storage process.
 5. A process forpurifying hydrogen gas containing organic substances, comprising:contacting hydrogen gas containing organic substances with ahydrogen-storage alloy, reacting the hydrogen gas with thehydrogen-storage alloy to form a hydrogen-containing alloy, thenallowing the hydrogen-containing alloy to release hydrogen gas, andcollecting the released hydrogen gas, wherein the hydrogen-storage alloyis the hydrogen-storage alloy according to claim 1.